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Title:
CATALYST
Document Type and Number:
WIPO Patent Application WO/2015/118100
Kind Code:
A1
Abstract:
The present invention provides novel catalysts of formula (I), where M1 and M2 are different and are independently selected from Mg, Zn, Fe, Co, Al and Cr, and catalyst systems comprising these catalysts. The invention also relates to the use of the inventive catalysts and catalyst systems to catalyse the reaction between i) carbon dioxide and an epoxide, ii) an epoxide and an anhydride, or iii) a lactide and/or a lactone. The invention also relates to a method for producing a catalyst of formula (I).

Inventors:
WILLIAMS CHARLOTTE (GB)
SAINI PRABHJOT (GB)
ROMAIN CHARLES (GB)
Application Number:
PCT/EP2015/052496
Publication Date:
August 13, 2015
Filing Date:
February 06, 2015
Export Citation:
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Assignee:
IMP INNOVATIONS LTD (GB)
International Classes:
B01J31/22; C08G64/34
Domestic Patent References:
WO2013034750A22013-03-14
WO2009130470A12009-10-29
Foreign References:
Other References:
P. K. SAINI ET AL: "Dinuclear metal catalysts: improved performance of heterodinuclear mixed catalysts for CO2-epoxide copolymerization", CHEMICAL COMMUNICATIONS, vol. 50, no. 32, 20 February 2014 (2014-02-20), pages 4164, XP055179323, ISSN: 1359-7345, DOI: 10.1039/c3cc49158g
Attorney, Agent or Firm:
KILBURN & STRODE LLP (London WC1R 4PJ, GB)
Download PDF:
Claims:
Claims

A catalyst of formula (I

wherein:

Mi and M2 are different and are independently selected from Mg, Zn, Fe, Co, Al and Cr;

R-i and R2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyi, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;

R3 is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene,

heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene,

heteroalkylene, heteroalkenylene and heteroalkynylene, may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;

R4 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;

R5 is H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;

Ei is C, E2 is O, S or NH or E^ is N and E2 is O;

X is independently selected from OC(0)Rx, OS02Rx, OSORx, OSO(Rx)2, S(0)Rx, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;

Rx is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl; and G is absent or independently selected from a neutral or anionic donor ligand which is a Lewis base.

2. The catalyst according to claim 1 , wherein M-i and M2 are independently selected from Mg, Zn, Fe and Co.

3. The catalyst according to claim 1 or claim 2, wherein M-i is either Mg or Zn.

4. The catalyst according to any preceding claim, wherein M-i is Zn and M2 is Mg.

5. The catalyst according to any preceding claim, wherein each occurrence of R2, R4 and R5 are H, R3 is an optionally substituted propylene, phenylene or cyclohexylene, E-i is C and E2 is O, S or NH. 6. The catalyst according to any preceding claim, wherein R-i is independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, silyl, sulfinate, and optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy or alkylthio.

7. The catalyst according to any preceding claim, wherein X is independently

OC(0)Rx, OS02Rx, OS(0)Rx, OSO(Rx)2, S(0)Rx, ORx, halide, nitrate, hydroxyl, carbonate, amino, nitro, amido, and optionally substituted alkyl, heteroalkyi, aryl or heteroaryl.

8. The catalyst according to any preceding claim, wherein Rx is independently optionally substituted alkyl, alkenyl, alkynyl, heteroalkyi, aryl, heteroaryl or alkylaryl.

9. The catalyst according to any preceding claim having the formula:

[L7M,M2(X)2G2] wherein either occurrence of G is either absent or present and wherein X, G M-i and M2 are as defined in any preceding claim, preferably wherein X is OAc or halide.

10. A catalyst system comprising a catalyst as defined in any of claims 1 to 9.

1 1 . The catalyst system according to claim 10, further comprising a second catalyst or a co-catalyst.

12. The catalyst system according to claim 1 1 , wherein the second catalyst is a compound of formula (lc):

wherein R-i to R5, E-i , E2, G and X are as defined in any of claims 1 to 8,

M-i and M2 may be the same or different, and are selected from the group consisting of

Zn(ll), Cr(ll), Co(ll), Mn(ll), Mg(ll), Fe(ll), Ti(ll), Cr(lll)-X, Co(lll)-X, Mn(lll)-X, Fe(lll)-X, Ca(ll), Ge(ll), Al(lll)-X, Ti(lll)-X, V(lll)-X, Ge(IV)-(X)2 and Ti(IV)-(X)2, preferably wherein the second catalyst is selected from [L1Mg2(OAc)2] and [L1Zn2(OAc)2].

13. A process for the reaction of:

(i) carbon dioxide with an epoxide;

(ii) an epoxide and an anhydride, or

(iii) a lactide and/or a lactone,

in the presence of a catalyst as claimed in any one of claims 1 to 9 or a catalyst system as claimed in any one of claims 10 to 12, optionally wherein the process is carried out in the presence of a chain transfer agent.

14. A product of the process of claim 13.

15. A process for the production of a catalyst as claimed in any one of claims 1 to 9, said process comprising the steps of:

a) Reacting a ligand of formula (lb):

with a compound of formula (IV):

n corresponds to the oxidation state of M-i;

RMi is independently selected from hydrogen, and optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, amino, alkoxy, aryloxy, alkylthio or alkylaryl; and

b) Reacting the product of step a) with a compound of formula (V):

M2(X)m (V)

m corresponds to the oxidation state of M2;

c) optionally adding a compound comprising G;

wherein R-i to R5, E-i, E2, M-i, M2, X and G are as defined in any of claims 1 to 9.

16. The process according to claim 15, wherein each RMi is independently selected from optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, amino, thioalkyi and alkylaryl.

17. A catalyst, catalyst system, product or process substantially as hereinbefore defined with reference to one or more of the examples.

Description:
Catalyst

Technical Field

The present invention relates to the field of polymerisation catalysts, and in particular heterometallic catalysts and mixtures thereof, and systems comprising said catalysts for polymerising carbon dioxide and an epoxide, a lactide and/or lactone, or an epoxide and an anhydride.

Background

Environmental and economic concerns associated with depleting oil resources have triggered a growing interest in the chemical conversion of carbon dioxide (C0 2 ), so as to enable its use as a renewable carbon source. C0 2 is, despite its low reactivity, a highly attractive carbon feedstock, as it is inexpensive, virtually non-toxic, abundantly available in high purity and non-hazardous. Therefore, C0 2 could be a promising substitute for substances such as carbon monoxide or phosgene in many processes. One of the developing applications of C0 2 is the copolymerization with epoxides to yield aliphatic polycarbonates, a field pioneered by Inoue ef al. more than 40 years ago (Inoue, S. ef al, J. Polym. Sci., Part B: Polym. Lett. 1969, 7, pp287). In WO2009/130470, the contents of which are incorporated herein by reference in their entirety, the copolymerisation of an epoxide with C0 2 using a catalyst of a class represented by formula (I) was described:

Among the epoxides employed in the copolymerization, cyclohexene oxide (CHO) received special interest, as the product, poly(cyclohexene carbonate) (PCHC) shows a high glass transition temperature and reasonable tensile strength. Propylene oxide has also received interest as it produces a polymer (polypropylene carbonate, known as PPC) with elastomeric properties which are useful in film applications. Kember ef al (Angew. Chem., Int. Ed., 2009, 48, pp931 and Inorg. Chem., 2009, 48, pp9535) reported an air- stable di-zinc acetate complex, coordinated by a macrocyclic ligand, falling within formula (I) above, which shows high catalytic activity, even at ambient C0 2 pressure. The catalyst exhibits excellent copolymerization selectivity, giving high proportions of carbonate repeat units and low yields of cyclic cyclohexene carbonate (CHC) by-product. The di-zinc acetate complex is a rare example of a catalyst that is capable of high activity at ambient pressure (1 bar) of C0 2 , yielding PCHC of moderate molecular weight, with narrow polydispersity index (PDI), and reaching remarkably high turnover numbers (TON). WO2013/034750, the contents of which are incorporated herein by reference in their entirety, discloses the copolymerisation of an epoxide with C0 2 in the presence of a chain transfer agent using a catalyst of a class represented by formula (I):

Various compounds according to formula (I) above were tested for their ability to catalyse the reaction between different epoxides and carbon dioxide. In each of these tested catalysts, both occurrences of M were the same (referred to hereinafter as homometallic catalysts). While WO2013/034750 contemplates that catalysts comprising two different metals (referred to hereinafter as heterometallic catalysts) could be used, such catalysts were not tested.

The inventors have now surprisingly found that heterometallic catalysts are also active as catalysts, and have activity which is comparable to, or better than either of the

corresponding homometallic catalysts alone or a 50:50 mixture thereof. For example, the inventors have found that a catalyst containing one zinc and one magnesium metal centre surprisingly has better activity that the corresponding di-zinc or di-magnesium catalysts, or a 50:50 mixture of the corresponding di-zinc and di-magnesium catalyst. The inventive heterometallic catalysts and systems comprising such catalyst also unexpectedly retain their selectivity and degree of control over the polymer produced. Thus, the present invention represents a novel and inventive selection over the prior art disclosures.

Summary of Invention

In the first aspect of the in rmula (I):

I)

wherein:

Mi and M 2 are different and are independently selected from Mg, Zn, Fe, Co, Al and

Cr;

R-i and R 2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;

R 3 is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene, may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;

R 4 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;

R 5 is H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;

Ei is C, E 2 is O, S or NH or E^ is N and E 2 is O;

X is independently selected from OC(0)R x , OS0 2 R x , OSOR x , OSO(R x ) 2 , S(0)R x , OR x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl; R x is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl; and

G is absent or independently selected from a neutral or anionic donor ligand which is a Lewis base.

In a second aspect of the invention, there is provided a catalyst system comprising a catalyst according to the first aspect and optionally a second catalyst and/or a co-catalyst.

In a third aspect of the invention, there is provided a process for the reaction of (i) carbon dioxide with an epoxide, (ii) an anhydride and an epoxide, or (iii) a lactide and/or a lactone in the presence of a catalyst according to the first aspect or a catalyst system according to the second aspect, optionally in the presence of a chain transfer agent.

The fourth aspect of the invention provides a product of the process of the third aspect of the invention.

The fifth aspect of the invention provides a method for the synthesis of a catalyst according to the first aspect, or a catalyst system according to the second aspect, the method comprising:

a) Reacting a ligand of formula (lb):

(lb)

with a compound of formula (IV):

n corresponds to the oxidation state of M-i ; R M i is independently selected from hydrogen, and an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, amino, alkoxy, aryloxy, alkylthio or alkylaryl; and

b) Reacting the product of step a) with a compound of formula (V):

M 2 (X) m (V)

wherein m corresponds to the oxidation state of M 2 ;

c) optionally adding a compound comprising G;

wherein R-i to R 5 , E-i , E 2 , M-i , M 2 , X and G are as defined for the catalyst of first aspect of the invention.

Brief Description of Figures

Embodiments of the invention are described below by way of example and with reference to the accompanying drawings in which: Figure 1 : MALDI-ToF mass spectrum for product of Example 1 a, Catalyst System 1 , with the structures for the molecular ions illustrated.

Figure 2: ESI- mass spectrum for product of Example 1 b, Catalyst System 2, with the structures for the molecular ions illustrated.

Figure 3: ESI- mass spectrum for product of Example 1 c, [L 4 ZnMg(OAc) 2 ], crystallised from Catalyst System 2, with the structures for the molecular ions illustrated.

Figure 4: ESI mass spectrum for product of Example 1 d, Catalyst System 3, with the structures for the molecular ions illustrated.

Figure 5: ESI mass spectrum for product of Example 1 e, Catalyst System 4, with the structures for the molecular ions illustrated. Figure 6: ESI mass spectrum for product of Example 1f, Catalyst System 5, with the structures for the molecular ions illustrated.

Figure 7: ESI mass spectrum for product of Example 1 g, Catalyst System 6, with the structures for the molecular ions illustrated.

Figure 8: MALDI-ToF mass spectrum for product of Example 1 h, Catalyst System 7, with the structures for the molecular ions illustrated. Figure 9: Comparison of 1 H NMR spectrum of Catalyst System 7 (top) and the product of Example 1 i, [L 1 MgZnBr 2 ] (bottom) indicating the differences in purity. Figure 10: MALDI-ToF mass spectrum for product of Example 1j, Catalyst System 8, with the structures for the molecular ions illustrated.

Figure 1 1 : MALDI-ToF mass spectrum for product of Example 1 k, Catalyst System 9, with the structures for the molecular ions illustrated.

Figure 12: MALDI-ToF mass spectrum for product of Example 11, Catalyst System 10, with the structures for the molecular ions illustrated.

Figure 13: MALDI-ToF mass spectrum for product of Example 1 m, Catalyst System 11 , with the structures for the molecular ions illustrated.

Figure 14: MALDI-ToF mass spectrum for product of Example 1 n, Catalyst System 12, with the structures for the molecular ions illustrated. Figure 15: MALDI-ToF mass spectrum for product of Example 1 o, Catalyst System 13, with the structures for the molecular ions illustrated.

Figure 16: 1 H NMR spectrum of crude CHO/C0 2 copolymerization reaction mixture used to calculate Catalyst System 1 's TON and TOF. The spectrum confirms the absence of signals due to cyclic carbonate (4 ppm) or ether linkages (3.4ppm) as by-products.

Figure 17: MALDI-ToF spectrum of the poly(cyclohexene carbonate) produced using Catalyst System 1. Figure 18: MALDI-ToF spectrum of the poly(cyclohexene carbonate) produced by using Catalyst System 1 , with 16 equivalents of water.

Definitions

For the purpose of the present invention, an aliphatic group is a hydrocarbon moiety that may be straight chain or branched and may be completely saturated, or contain one or more units of unsaturation, but which is not aromatic. The term "unsaturated" means a moiety that has one or more double and/or triple bonds. The term "aliphatic" is therefore intended to encompass alkyl, alkenyl or alkynyl groups, and combinations thereof. An aliphatic group is preferably a Ci -2 oaliphatic group, that is, an aliphatic group with 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an aliphatic group is a Ci-i 5 aliphatic, more preferably a Ci-i 2 aliphatic, more preferably a Ci_ 10 aliphatic, even more preferably a Ci -8 aliphatic, such as a Ci -6 aliphatic group.

An alkyl group is preferably a "Ci -2 o alkyl group", that is an alkyl group that is a straight or branched chain with 1 to 20 carbons. The alkyl group therefore has 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an alkyl group is a C 1-15 alkyl, preferably a C 1-12 alkyl, more preferably a C 1-10 alkyl, even more preferably a C^. 8 alkyl, even more preferably a C 1-6 alkyl group. Specifically, examples of "Ci -20 alkyl group" include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso- butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n- tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 1 ,1 -dimethylpropyl group, 1 ,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, 1- ethyl-2-methylpropyl group, 1 ,1 ,2-trimethylpropyl group, 1-ethylbutyl group, 1-methylbutyl group, 2-methylbutyl group, 1 ,1-dimethylbutyl group, 1 ,2-dimethylbutyl group, 2,2- dimethylbutyl group, 1 ,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group and the like.

Alkenyl and alkynyl groups are preferably "C 2-2 oalkenyl" and "C 2-2 oalkynyl", more preferably "C 2- i 5 alkenyl" and "C 2- i 5 alkynyl", even more preferably "C 2- i 2 alkenyl" and "C 2- i 2 alkynyl", even more preferably "C 2-10 alkenyl" and "C 2-10 alkynyl", even more preferably "C 2-8 alkenyl" and "C 2-8 alkynyl", most preferably "C 2-6 alkenyl" and "C 2-6 alkynyl" groups, respectively.

A heteroaliphatic group is an aliphatic group as described above, which additionally contains one or more heteroatoms. Heteroaliphatic groups therefore preferably contain from 2 to 21 atoms, preferably from 2 to 16 atoms, more preferably from 2 to 13 atoms, more preferably from 2 to 1 1 atoms, more preferably from 2 to 9 atoms, even more preferably from 2 to 7 atoms, wherein at least one atom is a carbon atom. Particularly preferred heteroatoms are selected from O, S, N, P and Si. When heteroaliphatic groups have two or more heteroatoms, the heteroatoms may be the same or different.

An alicyclic group is a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic (including fused, bridging and spiro-fused) ring system which has from 3 to 20 carbon atoms, that is an alicyclic group with 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an alicyclic group has from 3 to 15, more preferably from 3 to 12, even more preferably from 3 to 10, even more preferably from 3 to 8 carbon atoms, even more preferably from 3 to 6 carbons atoms. The term "alicyclic" encompasses cycloalkyl, cycloalkenyl and cycloalkynyl groups. It will be appreciated that the alicyclic group may comprise an alicyclic ring bearing one or more linking or non- linking alkyl substituents, such as -CH 2 -cyclohexyl. Specifically, examples of the C 3-2 o cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl and cyclooctyl.

A heteroalicyclic group is an alicyclic group as defined above which has, in addition to carbon atoms, one or more ring heteroatoms, which are preferably selected from O, S, N, P and Si. Heteroalicyclic groups preferably contain from one to four heteroatoms, which may be the same or different. Heterocyclic groups preferably contain from 5 to 20 atoms, more preferably from 5 to 14 atoms, even more preferably from 5 to 12 atoms.

An aryl group is a monocyclic or polycyclic ring system having from 5 to 20 carbon atoms. An aryl group is preferably a "Ce-12 aryl group" and is an aryl group constituted by 6, 7, 8, 9, 10, 1 1 or 12 carbon atoms and includes condensed ring groups such as monocyclic ring group, or bicyclic ring group and the like. Specifically, examples of "Ce-ιο aryl group" include phenyl group, biphenyl group, indenyl group, naphthyl group or azulenyl group and the like. It should be noted that condensed rings such as indan and tetrahydro naphthalene are also included in the aryl group. A heteroaryl group is an aryl group having, in addition to carbon atoms, from one to four ring heteroatoms which are preferably selected from O, S, N, P and Si. A heteroaryl group preferably has from 5 to 20, more preferably from 5 to 14 ring atoms. Specifically, examples of a heteroaryl group include pyridine, imidazole, methylimidazole and dimethylaminopyridine.

Examples of alicyclic, heteroalicyclic, aryl and heteroaryl groups include but are not limited to cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline, dioxin, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine,

napthyridine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazine, phenoxazine, phthalazine, piperazine, piperidine, pteridine, purine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran, triazine, triazole, and trithiane.

The term "halide" or "halogen" are used interchangeably and, as used herein mean a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably a fluorine atom, a bromine atom or a chlorine atom, and more preferably a fluorine atom.

A haloalkyl group is preferably a "Ci -2 o haloalkyl group", more preferably a "C - 5 haloalkyl group", more preferably a "C - 2 haloalkyl group", more preferably a "CMO haloalkyl group", even more preferably a "C 1-8 haloalkyl group", even more preferably a "C 1-6 haloalkyl group" and is a C 1 -2 o alkyl, a C 1-15 alkyl, a C 1-12 alkyl, a C 1-10 alkyl, a C 1-8 alkyl, or a C 1-6 alkyl group, respectively, as described above substituted with at least one halogen atom, preferably 1 , 2 or 3 halogen atom(s). Specifically, examples of "C1-20 haloalkyl group" include fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluroethyl group, trifluoroethyl group, chloromethyl group, bromomethyl group, iodomethyl group and the like.

An alkoxy group is preferably a "C1-20 alkoxy group", more preferably a "CM S alkoxy group", more preferably a "C1-12 alkoxy group", more preferably a "C1-10 alkoxy group", even more preferably a "Ci -8 alkoxy group", even more preferably a "Ci -6 alkoxy group" and is an oxy group that is bonded to the previously defined C1-20 alkyl, CM S alkyl, C1-12 alkyl, C 1-10 alkyl, C 1-8 alkyl, or C 1-6 alkyl group respectively. Specifically, examples of "C^. 20 alkoxy group" include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, iso-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, iso-hexyloxy group, , n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n- octadecyloxy group, n-nonadecyloxy group, n-eicosyloxy group, 1 ,1 -dimethylpropoxy group, 1 ,2-dimethylpropoxy group, 2,2-dimethylpropoxy group, 2-methylbutoxy group, 1- ethyl-2-methylpropoxy group, 1 ,1 ,2-trimethylpropoxy group, 1 ,1-dimethylbutoxy group, 1 ,2-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1 ,3- dimethylbutoxy group, 2-ethylbutoxy group, 2-methylpentyloxy group, 3-methylpentyloxy group and the like. An aryloxy group is preferably a "C5-20 aryloxy group", more preferably a "C6-12 aryloxy group", even more preferably a "Ce-ιο aryloxy group" and is an oxy group that is bonded to the previously defined C5-20 aryl, C 6 -12 aryl, or C 6- io aryl group respectively.

An alkylthio group is preferably a "C1-20 alkylthio group", more preferably a "CMS alkylthio group", more preferably a "C1-12 alkylthio group", more preferably a "CMO alkylthio group", even more preferably a "C 1-8 alkylthio group", even more preferably a "C 1-6 alkylthio group" and is a thio (-S-) group that is bonded to the previously defined C 1-2 o alkyl, C 1-15 alkyl, C 1-12 alkyl, C 1-10 alkyl, C 1-8 alkyl, or C 1-6 alkyl group respectively.

An arylthio group is preferably a "C5-2 0 arylthio group", more preferably a "C 6 -12 arylthio group", even more preferably a "C 6 -io arylthio group" and is an thio (-S-) group that is bonded to the previously defined C 5-2 o aryl, C 6- 12 aryl, or C 6- io aryl group respectively.

An alkylaryl group is preferably a "C6-12 aryl Ci -20 alkyl group", more preferably a preferably a "C6-12 aryl Ci-i 6 alkyl group", even more preferably a "C6-12 aryl Ci -6 alkyl group" and is an aryl group as defined above bonded at any position to an alkyl group as defined above. The point of attachment of the alkylaryl group to a molecule may be via the alkyl portion and thus, preferably, the alkylaryl group is -CH 2 -Ph or -CH 2 CH 2 -Ph. An alkylaryl group can also be referred to as "aralkyl".

A silyl group is preferably a group -Si(R S )3, wherein each R s can be independently an hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, each R s is independently hydrogen, or an unsubstituted aliphatic, alicyclic or aryl. Preferably, each R s is independently selected from hydrogen or an alkyl group selected from methyl, ethyl or propyl.

A silyl ether group is preferably a group OSi(R 6 )3 wherein each R 6 can be independently hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, each R 6 can be independently an hydrogen or unsubstituted aliphatic, alicyclic or aryl. Preferably, each R 6 is hydrogen or an alkyl group selected from methyl, ethyl or propyl. A nitrile group (also referred to as a cyano group) is a group CN. An imine group is a group -CRNR, preferably a group -CHNR 7 wherein R 7 is an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 7 is unsubstituted aliphatic, alicyclic or aryl. Preferably R 7 is an alkyl group selected from methyl, ethyl or propyl.

An acetylide group contains a triple bond -C≡C-R 9 , preferably wherein R 9 can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. For the purposes of the invention when R 9 is alkyl, the triple bond can be present at any position along the alkyl chain. In certain embodiments, R 9 is unsubstituted aliphatic, alicyclic or aryl. Preferably R 9 is methyl, ethyl, propyl or phenyl.

An amino group is preferably -NH 2 , -NHR 10 or -N(R 10 )2 wherein R 10 can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, a silyl group, aryl or heteroaryl group as defined above. It will be appreciated that when the amino group is N(R 10 )2, each R 10 group can be the same or different. In certain embodiments, each R 10 is independently an unsubstituted aliphatic, alicyclic, silyl or aryl. Preferably Rio is methyl, ethyl, propyl, SiMe 3 or phenyl.

An amido group is preferably -NRnC(O)- or -C(0)-NR i wherein R-n can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, Rn is unsubstituted aliphatic, alicyclic or aryl. Preferably Rii is hydrogen, methyl, ethyl, propyl or phenyl. The amido group may be terminated by hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.

An ester group is preferably -OC(0)Ri 2 - or -C(0)ORi 2 - wherein R 12 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 12 is unsubstituted aliphatic, alicyclic or aryl. Preferably R 12 is hydrogen, methyl, ethyl, propyl or phenyl. The ester group may be terminated by hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group. A sulfoxide is preferably -S(0)R 13 and a sulfonyl group is preferably -OS(0) 2 R 13 wherein R 13 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 13 is unsubstituted aliphatic, alicyclic or aryl. Preferably R 13 is hydrogen, methyl, ethyl, propyl or phenyl. A carboxylate group is preferably -OC(0)Ri 4 , wherein R 14 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R M is unsubstituted aliphatic, alicyclic or aryl. Preferably Ri 4 is hydrogen, methyl, ethyl, propyl, butyl (for example n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,

trifluoromethyl or adamantyl.

An acetamide is preferably MeC(0)N(R 15 ) 2 wherein R 15 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 15 is unsubstituted aliphatic, alicyclic or aryl. Preferably R 15 is hydrogen, methyl, ethyl, propyl or phenyl.

A phosphinate group is preferably a group -OP(0)(R 16 )2 or -P(0)(OR 16 ) wherein each R 16 is independently selected from hydrogen, or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 16 is aliphatic, alicyclic or aryl, which are optionally substituted by aliphatic, alicyclic, aryl or C-i. 6 alkoxy. Preferably R 16 is optionally substituted aryl or C 1-2 o alkyl, more preferably phenyl optionally substituted by Ci -6 alkoxy (preferably methoxy) or unsubstituted Ci -2 oalkyl (such as hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl).

A sulfinate group is preferably -OSOR1 7 wherein R 17 can be hydrogen, an aliphatic, heteroaliphatic, haloaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R1 7 is unsubstituted aliphatic, alicyclic or aryl. Preferably Ri 7 is hydrogen, methyl, ethyl, propyl or phenyl.

A carbonate group is preferably OC(0)ORi 8, wherein R 18 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 18 is optionally substituted aliphatic, alicyclic or aryl. Preferably R 18 is hydrogen, methyl, ethyl, propyl, butyl (for example n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, cyclohexyl, benzyl or adamantyl.

It will be appreciated that where any of the above groups are present in a Lewis base G, one or more additional R groups may be present, as appropriate, to complete the valency. For example, in the context of an amino group, an additional R group may be present to give RNHR-io. , wherein R is hydrogen, an optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. Preferably, R is hydrogen or aliphatic, alicyclic or aryl. Any of the aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, haloalkyl, alkoxy, aryloxy, alkylthio, arylthio, alkylaryl, silyl, silyl ether, ester, sulfoxide, sulfonyl, carboxylate, carbonate, imine, acetylide, amino, phosphinate, sulfonate or amido groups wherever mentioned in the definitions above, may optionally be substituted by halogen, hydroxy, nitro, carboxylate, carbonate, alkoxy, aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, amido, imine, nitrile, silyl, silyl ether, ester, sulfoxide, sulfonyl, acetylide, phosphinate, sulfonate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl groups (for example, optionally substituted by halogen, hydroxy, nitro, carbonate, alkoxy, aryloxy, alkylthio, arylthio, amino, imine, nitrile, silyl, sulfoxide, sulfonyl, phosphinate, sulfonate or acetylide).

It will be appreciated that although in formula (I), the groups X and G are illustrated as being associated with a single M-i or M 2 metal centre, one or more X and/or G groups may form a bridge between the M-i and M 2 metal centres.

For the purposes of the present invention, the epoxide substrate is not limited. The term epoxide therefore relates to any compound comprising an epoxide moiety. Preferred examples of epoxides for the purposes of the present invention include cyclohexene oxide, styrene oxide, propylene oxide, substituted cyclohexene oxides (such as limonene oxide, CioH 16 0 or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C 11 H 22 O), alkylene oxides (such as ethylene oxide and substituted ethylene oxides) or unsubstituted or substituted oxiranes (such as epichlorohydrin, 1 ,2-epoxybutane, glycidyl ethers), 2-(2- methoxyethoxy)methyl oxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl oxirane (ME3MO), 1 ,2- epoxybutane, glycidyl ethers), vinyl-cyclohexene oxide, 3-phenyl-1 ,2-epoxypropane, 1 ,2- and 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2,3-epoxy-1 ,2,3,4- tetrahydronaphthalene, indene oxide, and functionalized 3,5-dioxaepoxides. Examples of functionalized 3,5-dioxaepoxides include: o o o O

/ \ o . .0 0 , 0

1

Ph Ph The epoxide moiety may be a glycidyl ether or glycidyl carbonate. Examples of glycidyl ethers and glycidyl carbonates include:

glycidyl methyl ether

isopropyl glycidyl ether tert-butyl gly Xcidyl elher

butyl glycidyl ether

methoxyethyl glycidyl ether allyl gly idyl ether

henyl glycidyl ether benzyl glycidyl ether -tolyi gylcidol ether

glycidyl propargyl ether I'.-chloroethyl glycidyl ether fyrfuryl glycidyl elher

tetrahydrofurluryl glycidyl ether meth l glycidyl carbonate ethyl glycidyl carbonate

glycidyl benzoate cholestryl glycidyl carbonate

The epoxide substrate may contain more than one epoxide moiety, i.e. it may be a bis- epoxide, a tris-epoxide, or a multi-epoxide containing moiety. Examples of compounds including more than one epoxide moiety include bisphenol A diglycidyl ether and 3,4- epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. It will be understood that reactions carried out in the presence of one or more compounds having more than one epoxide moiety may lead to cross-linking in the resulting polymer.

The skilled person will appreciate that the epoxide can be obtained from "green" or renewable resources. The epoxide may be obtained from a (poly)unsaturated compound, such as those deriving from a fatty acid and/or terpene, obtained using standard oxidation chemistries. The epoxide moiety may contain -OH moieties, or protected -OH moieties. The -OH moieties may be protected by any suitable protecting group. Suitable protecting groups include methyl or other alkyl groups, benzyl, allyl, tert-butyl, tetrahydropyranyl (THP), methoxymethyl (MOM), acetyl (C(O)alkyl), benzolyl (C(O)Ph), dimethoxytrityl (DMT), methoxyethoxymethyl (MEM), p-methoxybenzyl (PMB), trityl, silyl (such as trimethylsilyl (TMS), f-Butyldimethylsilyl (TBDMS), f-Butyldiphenylsilyl (TBDPS), tri-/ ' so- propylsilyloxymethyl (TOM), and triisopropylsilyl (TIPS)), (4- methoxyphenyl)diphenylmethyl (MMT), tetrahydrofuranyl (THF), and tetrahydropyranyl (THP).

Preferably the epoxide is selected from propylene oxide, cyclohexene oxide and styrene oxide.

The epoxide preferably has a purity of at least 98%, more preferably >99%.

It will be understood that the term "an epoxide" is intended to encompass one or more epoxides. In other words, the term "an epoxide" refers to a single epoxide, or a mixture of two or more different epoxides. For example, the epoxide substrate may be a mixture of ethylene oxide and propylene oxide, a mixture of cyclohexene oxide and propylene oxide, a mixture of ethylene oxide and cyclohexene oxide, or a mixture of ethylene oxide, propylene oxide and cyclohexene oxide.

The skilled person will also understand that substituted and unsubstituted oxetanes can be used in place of, and in addition to, the epoxides of the second aspect of the invention. Suitable oxetanes include unsubstituted or substituted oxetanes (preferably substituted at the 3-position by halogen, alkyl (unsubstituted or substituted by -OH or halogen), amino, hydroxyl, aryl (e.g. phenyl), alkylaryl (e.g. benzyl)). Exemplary oxetanes include oxetane, 3-ethyl-3-oxetanemethanol, oxetane-3-methanol, 3-methyl-3-oxetanemethanol, 3- methyloxetane, 3-ethyloxetane, etc.

The term anhydride relates to any compound comprising an anhydride moiety in a ring system (i.e. a cyclic anhydride). Preferably, the anhydrides which are useful in the present invention have the following formula:

Wherein m" is 1 , 2, 3, 4, 5, or 6 (preferably 1 or 2), each R a1 , R a2 , R a3 and R a4 is independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl; or two or more of R a1 , R a2 , R a3 and R a4 can be taken together to form a saturated, partially saturated or unsaturated 3 to 12 membered, optionally substituted ring system, optionally containing one or more heteroatoms, or can be taken together to form a double bond. Each Q is independently C, O, N or S, preferably C, wherein R a3 and R a4 are either present, or absent, and can either be = or , according to the valency of Q. It will be appreciated that when Q is C, and is , R a3 and R a4 (or two R a4 on adjacent carbon atoms) are absent. Preferable anhydrides are set out below.

The term lactone relates to any cyclic compound comprising a-C(0)0- moiety in the ring. Preferably, the lactones which are useful in the present invention have the following formula:

Wherein m is 1 to 20 (e.g. 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 or 20), preferably 2, 4, or 5; and R L1 and R L2 are independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl. Two or more of R L1 and R L2 can be taken together to form a saturated, partially saturated or unsaturated 3 to 12 membered, optionally substituted ring system, optionally containing one or more heteroatoms. When m is 2 or more, the R L1 and R L2 on each carbon atom may be the same or different. Preferably R L1 and R L2 are selected from hydrogen or alkyl. Preferably, the lactone has the following structure:

The term lactide is a cyclic compound containing two ester groups. Preferably, the lactides which are useful in the present inve ing formula:

Wherein m' is 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10, (preferably 1 or 2, more preferably, 1 ) and R and R L4 are independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl. Two or more of R L3 and R L4 can be taken together to form a saturated, partially saturated or unsaturated 3 to 12 membered, optionally substituted ring system, optionally containing one or more heteroatoms, When m' is 2 or more, the R L3 and R L4 on each carbon atom may be the same or different or one or more R L3 and R L4 on adjacent carbon atoms can be absent, thereby forming a double or triple bond. It will be appreciated that while the compound has two moieties represented by (-CR L3 R L4 ) m ', both moieties will be identical. Preferably, m' is 1 , R L4 is H, and R L3 is H, hydroxyl or a C 1-6 alkyl, preferably methyl. The stereochemistry of the moiety represented by (-CR L3 R L4 ) m ' can either be the same (for example RR-lactide or SS-lactide), or different (for example, meso- lactide). The lactide may be a racemic mixture, or may be an optically pure isomer.

Preferably, the lactide has the following formula:

The term "lactone and/or lactide" used herein encompasses a lactone, a lactide and a combination of a lactone and a lactide. Preferably, the term "lactone and/or lactide" means a lactone or a lactide.

Preferred optional substituents of the groups R a1 , R a2 , R a3 , R a4 , R L1 , R L2 , R L3 and R L4 include halogen, nitro, hydroxyl, unsubstituted aliphatic, unsubstituted heteroaliphatic unsubstituted aryl, unsubstituted heteroaryl, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, and carboxylate.

Detailed Description

In the first aspect of the invention, there is provided a catalyst of formula (I):

wherein:

Mi and M 2 are different and are independently selected from Mg, Zn, Fe, Co, Al and

Cr;

Ri and R 2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;

R 3 is independently selected form optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene, may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;

R 4 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;

R 5 is H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;

Ei is C, E 2 is O, S or NH or Ei is N and E 2 is O;

X is independently selected from OC(0)R x , OS0 2 R x , OSOR x , OSO(R x ) 2 , S(0)R x , OR x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;

R x is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl; and

G is absent or independently selected from a neutral or anionic donor ligand which is a Lewis base.

The skilled person will understand that when M-i or M 2 is Mg or Zn, the metal(s) will be in the +2 oxidation state, i.e. Mg is Mg(l l) and Zn is Zn(ll). It will be understood that when M-i or M 2 is Co or Fe, the metal(s) can be in either the +2 or +3 oxidation state. In other words, Co can be either Co(l l) or Co(l l l), and Fe can be either Fe(l l) or Fe(l l l). When Fe and/or Co is in the +3 oxidation state, the catalyst of formula (I) will contain an additional X group co-ordinated to the metal centre, wherein X is as defined herein. When M-i or M 2 is Al or Cr, the metal(s) will be in the +3 oxidation state, i.e. Al is Al(l l l)-X and Cr is Cr(l ll)-X. Preferably M-i and M 2 are different and are independently selected from Mg, Zn, Fe and Co. Even more preferably, Mi is either Mg or Zn. In other words, for preferred catalyst of the invention, Mi is Zn and M 2 is Mg, Mi is Zn and M 2 is Co, Mi is Zn and M 2 is Fe, Mi is Mg and M 2 is Co, or Mi is Mg and M 2 is Fe. In highly preferred embodiments of the invention, Mi is Zn and M 2 is Mg.

Each occurrence of the groups R-i and R 2 may be the same or different. Preferably Ri and R 2 are independently selected from hydrogen, halide, amino, nitro, sulfoxide, silyl, sulfonyl, sulfinate, and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio. Preferably R 2 is hydrogen.

Even more preferably, each R 2 is hydrogen and Ri is independently selected from hydrogen, halide, amino, nitro, sulfoxide, silyl, sulfonyl, sulfinate and optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, such as hydrogen, d. 6 alkyl (e.g. haloalkyl), alkoxy, aryl, halide, nitro, silyl, sulfonyl and alkylthio, for example, 'Bu, iPr, Me, OMe, H, nitro, halogen, SiH 2 Me, SiEt 3 , S0 2 Me or phenyl. Preferably each occurrence of R 2 is the same, and each occurrence of Ri is the same, and Ri and R 2 can be the same or different.

It will be appreciated that the group R 3 is a disubstituted alkyl, alkenyl, alkynyl, heteroalkyi, heteroalkenyl or heteroalkynyl group which may optionally be interrupted by an aryl, heteroaryl, alicyclic or heteroalicyclic group, or may be a disubstituted aryl or cycloalkyl group which acts as a bridging group between two nitrogen centres in the catalyst of formula (I). Thus, where R 3 is a alkylene group, such as dimethylpropylene, the R 3 group has the structure -CH 2 -C(CH 3 ) 2 -CH 2 -. The definitions of the alkyl, aryl, cycloalkyl etc groups set out above therefore also relate respectively to the alkylene, arylene, cycloalkylene etc groups set out for R 3 and R 3 may be optionally substituted. Exemplary options for R 3 include ethylene, 2,2-dimethylpropylene, propylene, butylene, phenylene, cyclohexylene or biphenylene, more preferably 2,2-dimethylpropylene. When R 3 is cyclohexylene, it can be the racemic, RR- or SS- forms. Preferably R 3 is a substituted propylene, such as 2,2-di(alkyl)propylene.

Preferably each R 4 is independently selected from hydrogen, and an optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyi, heteroalkenyl, heteroalkynyl or heteroaryl.

Exemplary options for R 4 include H, Me, Et, Bn, iPr, tBu or Ph. A further exemplary option is -CH 2 -(pyridine). In particularly preferred embodiments, each R 4 is hydrogen.

Preferably each R 5 is independently selected from hydrogen, and optionally substituted aliphatic or aryl. More preferably, R 5 is selected from hydrogen, and optionally substituted alkyl or aryl. Exemplary R 5 groups include hydrogen, methyl, ethyl, phenyl and

trifluoromethyl, preferably hydrogen, methyl or trifluoromethyl. In particularly preferred embodiments, each R 5 is hydrogen.

Preferably Ei is C and E 2 is O, S or NH. In particularly preferred embodiments, Ei is C and E 2 is O.

Each X is independently selected from OC(0)R x , OS0 2 R x , OS(0)R x , OSO(R x ) 2 , S(0)R x , OR x , phosphinate, halide, nitro, hydroxyl, carbonate, amino, amido and optionally substituted aliphatic, heteroaliphatic (for example silyl), alicyclic, heteroalicyclic, aryl or heteroaryl. Preferably each X is independently OC(0)R x , OS0 2 R x , OS(0)R x , OSO(R x ) 2 , S(0)R x , OR x , halide, nitrate, hydroxyl, carbonate, amino, nitro, amido, alkyl (e.g. branched alkyl), heteroalkyl, (for example silyl), aryl or heteroaryl. In particularly preferred

embodiments, each X is independently OC(0)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OS0 2 R x . Preferred optional substituents for when X is aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl include halogen, hydroxyl, nitro, cyano, amino, or substituted or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl. Each X may be the same or different and preferably each X is the same. R x is independently hydrogen, or optionally substituted aliphatic, haloaliphatic,

heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl. Preferably, R x is optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl.

Preferred optional substitutents for R x include halogen, hydroxyl, cyano, nitro, amino, alkoxy, alkylthio, or substituted or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl (e.g. optionally substituted alkyl, aryl, or heteroaryl).

Exemplary options for X include OAc, OCOEt, OC(0)CF 3 , halogen, OSO(CH 3 ) 2 , Et, Me, OMe, OiPr, OtBu, CI, Br, I, F, N(iPr) 2 or N(SiMe 3 ) 2, OPh, OBn, salicylate, diphenyl phosphinate, bis-(4-methoxy)phenyl phosphinate, dioctyl phosphinate, OCOBn,

OCOCH 2 C 6 F 5 , OCO(CH 2 ) 5 CH 3 , OCO(CH 2 ) 7 CH 3 , OCO(CH 2 ) 9 CH 3 , 0(CH 2 ) 5 CH 3 ,

0(CH 2 ) 7 CH 3 , 0(CH 2 ) 9 CH 5 , etc.

When G is not absent, it is a group which is capable of donating a lone pair of electrons (i.e. a Lewis base). In certain embodiments, G is a nitrogen-containing Lewis base. Each G may be neutral or negatively charged. If G is negatively charged, then one or more positive counterions will be required to balance out the charge of the complex. Suitable positive counterions include group 1 metal ions (Na + , K + , etc), group 2 metal ions (Mg 2+ , Ca 2+ , etc), imidazolium ions, a positively charged optionally substituted heteroaryl, heteroaliphatic or heteroalicyclic group, ammonium ions (i.e. N(R 12 ) 4 + ), iminium ions (i.e. (R 12 ) 2 C=N(R 12 ) 2 + , such as bis(triphenylphosphine)iminium ions) or phosphonium ions (P(R 12 ) 4 + ), wherein each R 12 is independently selected from hydrogen or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl. Exemplary counterions include [H-B] + wherein B is selected from triethylamine, 1 ,8- diazabicyclo[5.4.0]undec-7-ene and 7-methyl-1 ,5,7-triazabicyclo[4.4.0]dec-5-ene.

G is preferably independently selected from an optionally substituted heteroaliphatic group, an optionally substituted heteroalicyclic group, an optionally substituted heteroaryl group, a halide, hydroxide, hydride, a carboxylate and water. More preferably, G is independently selected from water, an alcohol, a substituted or unsubstituted heteroaryl (imidazole, methyl imidazole (for example, N-methyl imidazole), pyridine, 4- dimethylaminopyridine, pyrrole, pyrazole, etc), an ether (dimethyl ether, diethylether, cyclic ethers, etc), a thioether, carbene, a phosphine, a phosphine oxide, a substituted or unsubstituted heteroalicyclic (morpholine, piperidine, tetrahydrofuran,

tetrahydrothiophene, etc), an amine, an alkyl amine trimethylamine, triethylamine, etc), acetonitrile, an ester (ethyl acetate, etc), an acetamide (dimethylacetamide, etc), a sulfoxide (dimethylsulfoxide, etc), a carboxylate, a hydroxide, hydride, a halide, a nitrate, a sulfonate, etc. In some embodiments, one or both instances of G is independently selected from optionally substituted heteroaryl, optionally substituted heteroaliphatic, optionally substituted heteroalicyclic, halide, hydroxide, hydride, an ether, a thioether, carbene, a phosphine, a phosphine oxide, an amine, an alkyl amine, acetonitrile, an ester, an acetamide, a sulfoxide, a carboxylate, a nitrate or a sulfonate. In certain embodiments, G may be a halide; hydroxide; hydride; water; a heteroaryl, heteroalicyclic or carboxylate group which are optionally substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro or nitrile. In preferred embodiments, G is independently selected from halide; water; a heteroaryl optionally substituted by alkyl (e.g. methyl, ethyl etc), alkenyl, alkynyl, alkoxy (preferably methoxy), halogen, hydroxyl, nitro or nitrile. In some embodiments, one or both instances of G is negatively charged (for example, halide). In further embodiments, one or both instances of G is an optionally substituted heteroaryl. Exemplary G groups include chloride, bromide, pyridine, methylimidazole (for example N-methyl imidazole) and dimethylaminopyridine (for example, 4-methylaminopyridine).

It will be appreciated that when a G group is present, the G group may be associated with a single M metal centre as shown in formula (I), or the G group may be associated with both metal centres and form a bridge between the two metal centres, as shown below in formula (la):

Wherein R 2 , R3, R 4 , R 5 , M, G, X, Ei and E 2 are as defined for formula (I).

It will be appreciated that the preferred features described above for the catalyst of the first aspect may be present in combination mutatis mutandis.

For example, in preferred embodiments of the first aspect, each occurrence of R 2 , R 4 and R 5 are H, R 3 is an optionally substituted propylene, phenylene or cydohexylene, is C and E 2 is O, S or NH (preferably E 2 is O). Preferably Mi, is Mg and M 2 is Zn (and vice versa).

Preferably, each occurrence of R 2 , R 4 and R 5 are H, R 3 is an optionally substituted propylene, phenylene or cydohexylene, is C and E 2 is O, S or NH (preferably E 2 is O), each X is independently OC(0)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OS0 2 R x , each R-i is independently hydrogen, alkyl, alkenyl, aryl, heteroaryl, alkoxy, alkylthio, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate or silyl, each G (where present) is independently selected from halide; water; a heteroaryl optionally substituted by alkyl (e.g. methyl, ethyl etc), alkenyl, alkynyl, alkoxy (preferably methoxy), halogen, hydroxyl, nitro or nitrile, and either M-i or M 2 is Mg or Zn (even more preferably is Zn and M 2 is Mg).

Exemplary catalysts of the first aspect are as follows:

[L 7 M!M2(X)2G 2 ]

wherein either occurrence of G is either absent or present, and preferably wherein X is independently OC(0)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OS0 2 R x , even more preferably X is OAc. Preferably M-i or M 2 is Mg or Zn and even more preferably M-i is Zn and M 2 is Mg (or vice versa).

In a second aspect of the invention, there is provided a catalyst system comprising a catalyst according to the first aspect.

The catalyst system of the second aspect may comprise one or more second catalysts which are capable of catalysing the reaction between (i) carbon dioxide and an epoxide, (ii) an epoxide and an anhydride or (iii) a lactide and/or a lactone, depending on the nature of the reaction to be carried out. Suitable second catalysts include the catalysts of formula (I) as described in WO 2009/130470 and the catalysts of formulae (I) or (III) as described in WO 2013/034750, the entire contents of which are hereby incorporated by reference. In other words, the second catalyst may be one or more of a catalyst of formula (lc):

wherein R-i to R 5 , E-i, E 2 , G and X are as described above for the first aspect, and wherein Mi and M 2 may be the same or different, and are selected from the group consisting of Zn(ll), Cr(ll), Co(ll), Mn(ll), Mg(ll), Fe(ll), Ti(ll), Cr(lll)-X, Co(lll)-X, Mn(lll)-X, Fe(lll)-X, Ca(ll), Ge(ll), Al(lll)-X, Ti(lll)-X, V(lll)-X, Ge(IV)-(X) 2 and Ti(IV)-(X) 2 .

The skilled person will understand that the preferred options for each of Ri to R 5 , E-i, E 2 , G and X as described for the first aspect apply equally to the second catalysts of formula (lc), and that the preferred features described above for each of Ri to R 5 , Ei, E 2 , G and X for the first aspect may be present in combination mutatis mutandis for the second catalysts. For the second catalysts, X is preferably a carboxylate such as acetate, benzoate and trifuloroacetate, or halide. For the second catalysts M-i and M 2 are preferably selected from Mg(ll), Zn(ll), Co(ll), Cr(ll), Fe(ll), Al(lll)-X, Co(lll)-X, Fe(lll)-X and Cr(lll)-X, even more preferably M-i and M 2 are selected from Mg(ll) and Zn(ll). Exemplary second catalysts include [L 1 Mg 2 (X) 2 ] and [L 1 Zn 2 (X) 2 ] wherein X is as defined for the first aspect of the invention, and is preferably OAc. Further exemplary second catalysts include [L 3 Mg 2 (X) 2 ], [L 3 Zn 2 (X) 2 ], [L 4 Mg 2 (X) 2 ], [L 4 Zn 2 (X 2 )], [L 5 Mg 2 (X) 2 ], [L 5 Zn 2 (X) 2 ], [L 6 Mg 2 (X) 2 ], [L 6 Zn 2 (X) 2 ], [L 7 Mg 2 (X) 2 ], [L 7 Zn 2 (X) 2 ], [L 1 Fe 2 (X) 2 ] and [L 1 Co 2 (X) 2 ]. The catalyst system of the second aspect may comprise a co-catalyst. Suitable co- catalysts include salts such as ammonium salts and phosphonium salts, or Lewis bases, such as dimethylaminopyridine (DMAP), methyl imidazole and pyridine. The catalyst system may comprise at least about 0.5% by weight, for example, from about 0.5 % by weight to about 99.5 % by weight of the catalyst according to the first aspect. Preferably the catalyst system comprises at least about 5% by weight, such as at least about 10% by weight, more preferably at least about 30% by weight, even more preferably at least about 50% by weight and even more preferably at least about 75% by weight, e.g. at least about 95% by weight of the catalyst according to the first aspect.

The second catalyst(s) may be present in an amount of from about 0.5 % by weight to about 99.5 % by weight of the catalyst system. For example, the second catalyst may be present in an amount of from about 1 % by weight to about 70% by weight, such as about 5% by weight to about 50% by weight, e.g. about 10% by weight to about 30% by weight, for example about 15% by weight to about 25% by weight of the catalyst system. When the co-catalyst is present, in may be present in the catalyst system in a molar ratio of from about 1 :1 to about 1 :100, co-catalyst:total catalyst content (i.e. sum of the catalyst of the first aspect and the second catalyst).

The catalysts of the first aspect and the catalyst system of the second aspect are capable of polymerising (i) carbon dioxide and an epoxide, (ii) an epoxide and an anhydride, and (iii) a lactide and/or a lactone. Therefore, in a third aspect of the invention there is provided a process for the reaction of carbon dioxide with an epoxide, an anhydride with an epoxide, or a lactide and/or a lactone in the presence of a catalyst according to the first aspect or a catalyst system according to the second aspect.

The process of the third aspect may be carried out in the presence of a chain transfer agent. Suitable chain transfer agents include the chain transfer agents, for example as defined by formula (II), in WO 2013/034750, the entire contents of which are hereby incorporated by reference. For example, the chain transfer agent may be water, or may comprise at least one amine (-NHR), alcohol (-OH) or thiol (-SH) moiety, wherein R is selected from hydrogen, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl, for example, selected from hydrogen, or optionally substituted alkyl, heteroalkyl, alkenyl, heteroalkenyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl.

The process of the third aspect may be carried out in the presence of a solvent.

Examples of solvents useful in the third aspect include toluene, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, etc.

When the process of the third aspect involves the reaction of an epoxide, the epoxide may be any compound comprising an epoxide moiety. The epoxide may be purified (for example by distillation, such as over calcium hydride) prior to reaction with carbon dioxide or the anhydride. For example, the epoxide may be distilled prior to being added to the reaction mixture comprising the catalyst or catalyst system. The process of the third aspect of the invention may be carried out at a pressure of 1 to 100 atmospheres, preferably at 1 to 40 atmospheres, such as at 1 to 10 atmospheres, more preferably at 1 or 2 atmospheres. The catalysts and catalyst systems used in the process of the third aspect allow the reaction to be carried out at low pressures. The catalysts of the first aspect or the catalyst systems of the second aspect may operate at temperatures of up to 250°C. The process of the third aspect of the invention may be carried out at a temperature of about 0°C to about 250°C, such as from about 0°C to about 120°C, preferably from about 50 ° C to about 100 ° C. The duration of the process may be up to 168 hours, such as from about 1 minute to about 24 hours, for example from about 5 minutes to about 12 hours, e.g. from about 1 to about 6 hours.

The process of the third aspect of the invention may be carried out at low catalytic loading. For example, when the reaction involves copolymerisation of carbon dioxide and an epoxide, the catalytic loading for the process is preferably in the range of 1 :1 ,000-100,000 catalyst:epoxide, more preferably in the region of 1 :1 ,000-50,000 catalyst:epoxide, even more preferably in the region of 1 :1 ,1000-10,000, and most preferably in the region of 1 :10,000 catalyst:epoxide. When the process involves copolymerisation of an epoxide and an anhydride, or the reaction of a lactide and/or lactone, the catalytic loading for the process is preferably in the range of 1 :1 ,000-100,000 catalyst: total monomer content, more preferably in the region of 1 :1 ,000-50,000 catalyst: total monomer content, even more preferably in the region of 1 :1 ,1000-10,000, and most preferably in the region of 1 :10,000 catalyst:total monomer content. The ratios above are molar ratios.

It will be appreciated that the various features described above for the process of the third aspect may be present in combination mutatis mutandis. All preferred features of the first and second aspects apply equally to the third aspect and may be present in combination mutatis mutandis. The fourth aspect of the invention provides a product of the process of the third aspect of the invention. All preferred features of the third aspect of the invention apply to the fourth aspect of the invention mutatis mutandis.

The fifth aspect of the invention provides a method for the synthesis of a catalyst according to the first aspect, or a catalyst system according to the second aspect, the method comprising:

a) Reacting a ligand of formula (lb):

(lb)

with a compound of formula (IV):

wherein n corresponds to the oxidation state of M-i;

RMI is independently selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, amino, alkoxy, aryloxy, alkylthio and alkylaryl; and

b) Reacting the product of step a) with a compound of formula (V):

M 2 (X) m (V)

wherein m corresponds to the oxidation state of M 2 ;

c) optionally adding a compound comprising G;

wherein Ri to R 5 , E-i, E 2 , M-i, M 2 , X and G are as defined for the catalyst of first aspect of the invention.

The skilled person will understand that the definitions of the groups R-i to R 5 , E-i, E 2 , X, G Mi and M 2 in the fifth aspect of the invention correspond to the definitions of the groups R-i to R 5 , EL E 2 , X, Mi and M 2 in the catalyst of the first aspect to be produced by the method. Preferably Μ-ι is Zn or Mg, and even more preferably M-i is Zn and M 2 is Mg. However, the skilled person will appreciate that for the method of the fifth aspect, the labelling of the metal atom can be switched such that M 2 is preferably Zn or Mg, and even more preferably M-i is Mg and M 2 is Zn.

The compound of formula (IV) may be any organometallic compound comprising M-|. The term "organometallic" is intended to cover compounds having a M C bond, as well as compounds having an M S bond, an M N bond and/or an M O bond. Preferably R M i may be independently selected from optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, amino, thioalkyl and alkylaryl. R M i may be the same of different.

Exemplary options for R M i include Me, Et, n-Pr, iPr, N-Bu, tBu, ethylhexyl, hexyl, octyl, cyclohexyl, benzyl (Bn), adamantyl, OEt, OPh, C(SiMe 3 ) 3 , N(SiMe 3 ) 2 , N(SiHMe 2 ) 2 , N(SiH 2 Me) 2 and N(SiH 3 ) 2 . For example, when Mi is Zn, the compound of formula (IV) may be Et 2 Zn or EtZnOEt.

The compound of formula (IV) may be added in a ratio of about 1 :0.01 to about 0.01 :1 , such as about 1 :1 relative to the ligand of formula (lb). The compound of formula (V) may be added in a ratio of about 1 :0.01 to about 0.01 :1 , such as about 1 :1 relative to the ligand of formula (lb).

The process of the fifth aspect may be carried out in the presence of a solvent. Examples of solvents useful in the fifth aspect include toluene, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, tetrahydrofuran (THF), pyridine, acetonitrile, etc.

The skilled person will appreciate that when G is present, it may be added to the reaction at any point. If the reaction is carried out in a solvent, G may be present in the solvent used (i.e. the solvent and G may be THF, pyridine or acetonitrile). The skilled person will also appreciate that when G is negatively charged, then one or more positive counterions will be required to balance out the charge of the compound added to the process. Suitable counterions are as described above for the first aspect. For example, if G is CI " , then the compound to be added to the process may be bis(triphenylphosphine) iminium chloride (PPNCI), Et 3 NHCI or KCI. Step a) of the process of the fifth aspect of the invention may be carried out at a temperature of from about -80°C to about 100°C. The duration of step a) may be up to 24 hours, such as from about 1 minute to about 12 hours.

Step b) of the process of the fifth aspect of the invention may be carried out at a temperature of from about -80 ° C to about 100 ° C. The duration of step b) may be up to 24 hours, such as from about 1 minute to about 12 hours.

Purely by way of example of the method of the fifth aspect, when the catalyst to be produced is [L 1 ZnMg(OAc) 2 ], the method of the fifth aspect involves a) reacting the compound H 2 L 1 with a compound Zn(R M i )2, and then b) subsequently reacting the product of step a) with Mg(OAc) 2 .

H 2 L' [L'ZnMgiOAc ]

cheme 1 : Example of process of the fifth aspect

Examples

Example 1

Materials

The synthesis of the macrocyclic pro-ligands H 2 L n were carried out as previously reported (M. R. Kember ef al, Angew. Chem. Int. Ed., 2009, 48, 931-933). The synthesis of metal complexes and catalyst systems were carried out under anhydrous conditions, using either a Schlenk line or a nitrogen-filled glovebox. Catalysts A and B were synthesised according to literature procedure (M. R. Kember, P. D. Knight, P. T. R. Reung and C. K. Williams, Angew. Chem. Int. Ed., 2009, 48, 931 -933, 1. M. R. Kember et al, Angew. Chem. Int. Ed., 2009, 48, 931 -933, M. R. Kember and C. K. Williams, J. Am. Chem. Soc, 2012, 134, 15676-15679). All solvents and reagents were obtained from Sigma Aldrich and Strem. THF was dried by refluxing over sodium and benzophenone and stored under nitrogen. Cyclohexene oxide (CHO) was dried over MgS0 4 and fractionally distilled under nitrogen. All dry solvents and reagents were stored under nitrogen and degassed by several freeze-pump-thaw cycles. Research grade carbon dioxide was used for copolymerization studies. The high pressure copolymerization reactions were carried out in a Parr 5513 100 ml. bench reactor.

1 H and 13 C{ 1 H} NMR spectra were recorded on a Bruker AV-400 instrument, unless otherwise stated. All mass spectrometry measurements were performed using a MALDI micro MX micromass instrument. The matrix used was dithranol with KOAc as the ionising agent and THF as the solvent. Elemental Analysis was determined by Stephen Boyer at London Metropolitan University and Alan Dickerson at Cambridge University. Size exclusion chromatography was recorded by a Polymer labs PL GPC-50 instrument. THF was used as the eluent, at a flow rate of 1 mLmin "1 . Two polymer labs mixed D columns were used and calibration was carried out by using narrow M w polystyrene standards.

1. Preparation of catalysts a) Preparation of Catalyst System 1

H 2 L 1 [L 1 ZnMg(OAc) 2 ] H 2 L 1 (0.60 g, 1.09 mmols) was dissolved in dry THF (30 mL) and cooled to -20 °C. Et 2 Zn (0.14 g, 1 .09 mmols) was dissolved in dry THF (10 mL) and cooled to -20 °C. The Et 2 Zn solution was added dropwise to the pro-ligand solution, at -20 °C and was allowed to warm, over 4 h, to 25 °C. Then, Mg(OAc) 2 (0.16 g, 1.09 mmols) was added to the reaction mixture and this was left to stir for 16 h. The solvent was removed under vacuum to produce a white solid (0.70 g, 85%). Calc. for C 3 8H 6 o0 2 N 2 MgZn : C, 60.17; H, 7.97; N, 7.39; Found: C, 59.88; H, 7.87; N, 7.31 %; MS (MALDI-TOF): m/z 697 ([L 1 MgZn(OAc)] + , 100%), 657 ([L 1 Mg 2 (OAc)] + , 25%), 739 ([L 1 Zn 2 (OAc)] + , 45%); 13 C NMR (400 MHz, C 6 D 6 ): 5C =176.2, 163.5, 135.6, 125.9, 123.6, 62.3, 56.2, 34.2, 32.1 , 27.9, 26.5, 24.4, 20.9 ppm. b) Preparation of Catalyst System 2

[L 4 MgZn(OAc) 2 ]

H 2 L 4 (0.2 g, 0.3 mmol) was dissolved in dry THF (5mL) under nitrogen at 25 °C. Et 2 Zn (0.037g, 0.3mmol) was dissolved in dry THF (2 mL), added to the ligand solution and stirred overnight. Mg(OAc)2 (0.043g, 0.3 mmol) was added and the solution stirred for a further 4 hours. The solvent was removed under vacuum to yield a white solid (0.23g, 0.27 mmol, 90%). MS (ESI): m/z 799.3 (100%, [L 4 MgZn(0 2 CH)] + ), 813.4 (20%, [L 4 MgZn(OAc)] + ), 759.4 (10%, [L 4 Mg2(0 2 CH)] + ), 841 .3 (15%, [L 4 Zn 2 (0 2 CH)] + ).

ESI-MS spectra run in MeCN containing (0.1 % NH 4 + 0 2 CH " ); see Figure 2. c) Preparation of rL 4 ZnMq(OAc)21 from Catalyst System 2

Catalyst System 2

Catalyst System 2 (0.15g) was dissolved in 2ml_ MeOH and placed in an NMR tube with a stopper. Large colourless crystals grew overnight and were filtered off. The crystals were analysed by ESI-MS (in MeCN with 0.1 % NH 4 + 0 2 CH " ); see Figure 3, which showed almost a complete disappearance of the peaks corresponding to the two homo-bimetallic compounds, [L 4 Mg 2 (OAc) 2 ] and [L 4 Zn 2 (OAc) 2 ] indicating the compound contains almost pure (>95%) hetero-bimetallic compound [L 4 MgZn(OAc) 2 ]. MS (ESI): m/z 799.3 (100%, [L 4 MgZn(0 2 CH)] + ), 813.4 (50%, [L 4 MgZn(OAc)] + ), 759.4.

ESI-MS spectra run in MeCN containing (0.1 % NH 4 + 0 2 CH " ); see Figure 3. d) Preparation of Catalyst system 3

H 2 L 5 [L 5 MgZn(OAc) 2 ]

H 2 L 5 (0.5 g, 1 .01 mmol) was dissolved in dry THF (10 mL) under nitrogen at 25 °C. Et 2 Zn (0.124 g, 1.01 mmol) was dissolved in dry THF (3 mL), added to the ligand solution and stirred overnight. Mg(OAc) 2 (0.143g, 1.01 mmol) was added along with MeOH (5 mL) and the solution stirred for a further 4 hours. The solvent was removed under vacuum to yield a white solid (0.62g, 0.88 mmol, 89%). MS (ESI): m/z 627.3 (100%, [L 5 MgZn(0 2 CH)] + ), 641.3 (60%, [L 5 MgZn(OAc)] + ), 587.3 (15%, [L 5 Mg2(0 2 CH)] + ), 601.3 (10%, [L 5 Mg2(OAc)] + ), 667.3 (40%, [L 5 Zn 2 (0 2 CH)] + ), 681.2 (40%, [L 5 Zn 2 (OAc)] + ).

ESI-MS spectra run in MeCN containing (0.1 % NH 4 + 0 2 CH " ); see Figure 4. e) Preparation of Catalyst System 4

H,L 6 [L 6 MgZn(0Ac) 2 ]

H 2 L 6 (0.33 g, 0.58 mmol) was dissolved in dry THF (5 mL) under nitrogen at 25 °C. Et 2 Zn (0.071 g, 0.58 mmol) was dissolved in dry THF (3 mL), added to the ligand solution and stirred overnight. Mg(OAc) 2 (0.082 g, 0.58 mmol) was added along with MeOH (5 mL) and the solution stirred for a further 4 hours. The solvent was removed under vacuum to yield a white solid (0.4g, 0.52 mmol, 89%). MS (ESI): m/z 707.4 (100%, [L 6 MgZn(0 2 CH)] + ), 667.3 (10%, [L 6 Mg 2 (0 2 CH)] + ), 747.2 (30%, [L 6 Zn 2 (0 2 CH)] + ).

ESI-MS spectra run in MeCN containing (0.1 % NH 4 + 0 2 CH " ); see Figure 5. f) Preparation of Catalyst System 5

H 2 L 7

H 2 L 7 (0.37 g, 0.70 mmol) was dissolved in dry THF (5 mL) under nitrogen at 25 °C. Et 2 Zn (0.087 g, 0.70 mmol) was dissolved in dry THF (3 mL), added to the ligand solution and stirred overnight. Mg(OAc) 2 (0.10 g, 0.70 mmol) was added along with MeOH (1 ml.) and the solution stirred for a further 4 hours. The solvent was removed under vacuum to yield a white solid (0.38g, 0.52 mmol, 74%). MS (ESI): m/z 677.2 (90%, [L 7 MgZn(OAc)] + ), 637.3 (100%, [L 7 Mg 2 (OAc)] + ), 717.1 (50%, [L 6 Zn 2 (OAc)] + ).

ESI-MS spectra run in MeCN containing (0.1 % NH 4 + 0 2 CH " ); see Figure 6. g) Preparation of Catalyst System 6

H 2 L 3 [L 3 MgZn(OAc) 2 ] H 2 L 3 (0.34 g, 0.67 mmol) was dissolved in dry THF (5 ml.) under nitrogen at 25 °C. Et 2 Zn (0.083 g, 0.67 mmol) was dissolved in dry THF (3 ml_), added to the ligand solution and stirred overnight. Mg(OAc) 2 (0.096 g, 0.67 mmol) was added along with MeOH (1 ml.) and the solution stirred for a further 4 hours. The solvent was removed under vacuum to yield a white solid (0.42g, 0.60 mmol, 90%). MS (ESI): m/z 631.2 (5%, [L 3 MgZn(0 2 CH)] + ), 645.3 (30%, [L 3 MgZn(OAc)] + ), 591.3 (10%, [L 3 Mg 2 (0 2 CH)] + ), 605.4 (100%, L 3 Mg 2 (OAc)] + ), 673.2 (10%, L 3 Zn 2 (0 2 CH)] + ), 685.2 (75%, L 3 Zn 2 (OAc)] + ).

ESI-MS spectra run in MeCN containing (0.1 % NH 4 + 0 2 CH " ); see Figure 7. h) Preparation of Catalyst System 7 (-65% rL 1 MqZnBr?1)

L MgZnBr 2

H 2 L 1 (0.1 12 g, 0.2 mmol) was dissolved in dry THF (10 mL) under nitrogen at 25 °C. Et 2 Zn (20 μΙ_, 0.2 mmol) was added to the ligand solution and stirred overnight. Pyridine solvent was added (5 mL), followed by a solution of MgBr 2 (0.038 g, 0.2 mmol) in a mixed THF (15 mL)/pyridine (5 mL) solvent system. The solution was stirred for 1 hour and the solvent was subsequently removed under vacuum to yield an off-white solid (0.158 g, 98 %).

MALDI-ToF spectra (Figure 8) run using dithranol matrix with KCI as the ionising agent and THF as the solvent: m/z 677.5 [LMg 2 Br] + , 717.4 [LMgZnBr] + , 757.4 [LZn 2 Br] + .

In this case the 1 H NMR spectrum (Figure 9, top) could be easily interpreted and compared to those of the two homo-bimetallic compounds [L 1 Mg 2 Br 2 ] and [L 1 Zn 2 Br 2 ]. Analysis of the 1 H NMR integrals confirm the Catalyst System 7 contains ~ 65% hetero- bimetallic [L 1 MgZnBr 2 ]. i) Preparation of rL 1 MqZnBr 2 l (>95%)

L 1 MgZnBr 2 >95%

H 2 L 1 (0.1 12 g, 0.2 mmol) was weighed into a Schlenk flask and dissolved in dry THF (10 mL) Et 2 Zn was subsequently added (20 μί, 0.2 mmol) and the reaction mixture was stirred overnight. Pyridine (5 mL) was subsequently added and the reaction medium was cooled to -78°C. To this, a solution of MgBr 2 (0.0375 g, 0.204 mmol) in pyridine (5 mL)/THF (15 mL) was added dropwise over a period of 15 minutes. Once the addition was finished, the reaction was allowed to stir for 15 minutes, and then the dry ice bath was removed. After a further 30 minutes, all solvent was removed in vacuo, affording a pale yellow powder. The product was dried in vacuo for 2 hours to yield a pale yellow solid (0.0910 g, 51 %). MALDI-ToF spectra run using dithranol matrix with KCI as the ionising agent and THF as the solvent: m/z 677.5 [LMg 2 Br] + , 717.4 [LMgZnBr] + , 757.4 [LZn 2 Br] + . The 1 H NMR spectrum (Figure 9, bottom) demonstrates the almost complete disappearance of peaks which are known to correspond to [L 1 Mg 2 Br 2 ] and [L 1 Zn 2 Br 2 ]. j) Preparation of Catalyst System 8

L 1 MgZnl 2

H 2 L 1 (0.1 12 g, 0.2 mmol) was dissolved in dry THF (5 mL) under nitrogen at 25 °C. Et 2 Zn (20 μί, 0.2 mmol) was subsequently added to the ligand solution and stirred overnight. Pyridine solvent was added (5 mL), followed by a turbid solution of Mgl 2 (0.057 g, 0.2 mmol) in a mixed THF (15 mL)/pyridine (5 mL) solvent system. The solution was stirred for 90 minutes and the solvent was subsequently removed under vacuum to yield a pale yellow solid (0.046 g, 25 %).

MALDI-ToF spectra (Figure 10) run using dithranol matrix with KCI as the ionising agent and THF as the solvent: m/z 725.7 [LMg 2 l] + , 765.7 [LMgZnl] + , 805.6 [LZn 2 l] + . k) Preparation of Catalysts System 9

L 1 FeZn(OAc) 2

H 2 L 1 (0.179 g, 0.3 mmol) was dissolved in dry THF (12.5 mL) under nitrogen at 25 °C. Et 2 Zn (33 L, 0.3 mmol) was subsequently added to the ligand solution and stirred overnight. Pyridine solvent was added (2.5 mL), followed by the dropwise addition of a yellow/brown solution of Fe(OAc) 2 (0.057 g, 0.3 mmol) in a mixed THF (7.5 mL)/pyridine (1 mL) solvent system. The solution was stirred for 1 hour, over which time a colour change from yellow/brown to brown occurred. All solvent was subsequently removed under vacuum to yield a brown powder (0.142 g, 55 %).

MALDI-ToF spectra (Figure 1 1 ) run using dithranol matrix with KCI as the ionising agent and THF as the solvent: m/z 721 .5 [LFe 2 (OAc)] + , 729.5 [LFeZn(OAc)] + , 737.5 [LZn 2 (OAc)] + .

I) Preparation of Catalyst System 10

L 1 FeZnCI 2

H 2 L 1 (0.179 g, 0.3 mmol) was dissolved in dry THF (10 mL) under nitrogen at 25 °C. Et 2 Zn (33 μί, 0.3 mmol) was subsequently added to the ligand solution and stirred overnight. Pyridine solvent was added (2.5 mL), followed by the dropwise addition of a yellow solution of FeCI 2 (0.041 g, 0.3 mmol) in a mixed THF (7.5 mL)/pyridine (2.5 mL) solvent system. The solution was stirred for 1 hour, over which time a colour change from yellow to brown occurred. All solvent was subsequently removed under vacuum to yield a brown powder (0.181 g, 75 %).

MALDI-ToF spectra (Figure 12) run using dithranol matrix with KCI as the ionising agent and THF as the solvent: m/z 697.5 [LFe 2 CI] + , 705.5 [LFeZnCI] + , 713.5 [LZn 2 CI] + . m) Preparation of Catalyst System 1 1

L 1 FeZnBr 2

H 2 L 1 (0.179 g, 0.3 mmol) was dissolved in dry THF (12.5 mL) under nitrogen at 25 °C. Et 2 Zn (33 μί, 0.3 mmol) was subsequently added to the ligand solution and stirred overnight. Pyridine solvent was added (2.5 mL), followed by the dropwise addition of a brown/yellow suspension of FeBr 2 (0.070 g, 0.3 mmol) in a mixed THF (9 mL)/pyridine (1 mL) solvent system. The solution was stirred for 1 hour, over which time a colour change to an orange/brown suspension was observed. All solvent was subsequently removed under vacuum to yield a brown powder (0.157 g, 58 %). MALDI-ToF spectra (Figure 13) run using dithranol matrix with KCI as the ionising agent and THF as the solvent: m/z 741.4 [LFe 2 Br] + , 749.4 [LFeZnCI] + , 757.4 [LZn 2 CI] + . n) Preparation of Catalyst System 12

L 1 CoZn(OAc) 2

H 2 L 1 (0.179 g, 0.3 mmol) was dissolved in dry THF (10 mL) under nitrogen at 25 °C. Et 2 Zn (33 μΙ_, 0.3 mmol) was subsequently added to the ligand solution and stirred overnight. Pyridine solvent was added (2.5 mL), followed by the dropwise addition of a purple solution of Co(OAc) 2 (0.057 g, 0.3 mmol) in a mixed THF (10 mL)/pyridine (2.5 mL) solvent system. The solution was stirred for 1 hour, over which time a colour change from pink to brown occurred. All solvent was subsequently removed under vacuum to yield a brown powder (0.172 g, 67 %).

MALDI-ToF spectra (Figure 14) run using dithranol matrix with KCI as the ionising agent and THF as the solvent: m/z 727.5 [LCo 2 (OAc)] + , 732.5 [LCoZn(OAc)] + , 737.5 [LZn 2 (OAc)] + . o) Preparation of Catalyst System 13

L 1 CoZnl 2 H 2 L 1 (0.179 g, 0.3 mmol) was dissolved in dry THF (12.5 mL) under nitrogen at 25 °C. Et 2 Zn (33 μΙ_, 0.3 mmol) was subsequently added to the ligand solution and stirred overnight. Pyridine solvent was added (2.5 mL), followed by the dropwise addition of a blue/green suspension of Col 2 (0.101 g, 0.3 mmol) in a mixed THF (27.5 mL)/pyridine (2.5 mL) solvent system. The solution was stirred for 1 hour, over which time a purple solution was formed. All solvent was subsequently removed under vacuum to yield a purple powder (0.234 g, 78 %).

MALDI-ToF spectra (Figure 15) run using dithranol matrix with KCI as the ionising agent and THF as the solvent: m/z 795.4 [LCo 2 l] + , 800.4 [LCoZnl] + , 805.4 [LZn 2 l] + . p) Preparation of Catalyst System 14

L 1 MgZnPh 2

H 2 L 1 (0.1 g, 0.181 mmol) was dissolved in dry THF (10 mL) and placed in the glovebox freezer (-40 °C). 0.26 mL of n-butyl-sec-butylmagnesium solution (0.7 M in hexane) was added to the THF solution dropwise. Then after four hours Ph 2 Zn (40 mg) was added to the solution and left to stir for 16 h at 25 °C in the glovebox. The solvent was then evaporated to produce a off-white solid. ().Calc. for C 46 H 6 4MgN 4 0 2 Zn: C, 69.52; H, 8.12;

N, 7.05 %. Found: C, 69.31 ; H, 7.85; N, 6.88 %. MALDI-ToF MS m/z: 675.4 (30%,

[L 1 MgZnPh] + ), 715.3 (60%, [L 1 MgZnPh] + ), 755.3 (40%, [L 1 Zn 2 Ph] + ). Due to the air sensitive nature of this compound many decomposition products were also observed in the mass spectrum.

Results

The characterization data for the mixed metal Catalyst Systems was different to either of the corresponding homo-bimetallic species. . An example of the analysis is given for Catalyst System 1 , in comparison with L 1 Zn 2 (OAc) 2 (Catalyst A) and L 1 Mg 2 (OAc) 2 (Catalyst B).

The 1 H NMR spectrum of the Catalyst System 1 (Figure 16) showed the complete consumption of the zinc bound ethyl group and the formation of broadened ligand resonances which are consistent with metal coordination. These broad signals could not be resolved either by changing solvent (e.g. benzene, toluene, tetrachloroethane) or by high/low temperature experiments (-50 to 80 °C). This is in contrast to the homodinuclear complexes A and B which both show clearly resolved peaks at elevated temperatures. Elemental analysis showed that the product contained equal quantities of Zn and Mg, as expected. The MALDI-ToF spectrum (Figure 1 ) showed a peak at 697 amu, which corresponds to the heterodinuclear Zn/Mg complex cation [LZnMg(OAc)] + . It has previously observed that this class of complexes are ionized during MALDI-ToF experiments to yield the cations resulting from the loss of a carboxylate co-ligand (M. R. Kember and C. K. Williams, J. Am. Chem. Soc, 2012, 134, 15676-15679, and M. R.

Kember, P. D. Knight, P. T. R. Reung and C. K. Williams, Angew. Chem.-lnt. Edit, 2009, 48, 931-933). The MALDI-ToF mass spectrum also indicated the presence of both homodinuclear complexes A and B, as evidenced by the peaks at 657 and 739 amu, due to [LMg 2 (OAc)] + and [LZn 2 (OAc )] + , respectively.

In order to rule out the possibility of the mixed metal species being formed only during the MALDI-ToF experiments, an equimolar mixture of A and B was compared. The equimolar mixture of complexes shows only ions associated with the two homodinuclear complexes (i.e. A and B); there is no evidence for any heterodinuclear complex cations. Furthermore, when the equimolar mixture was heated at 80 °C for 16 h (equivalent conditions as during polymerization), the spectrum remained the same, showing only the two homodinuclear complexes.

It was not possible to quantify the mixture composition due to the broad NMR signals, although the expected stoichiometry would be 1 :2:1

([L 1 Zn 2 (OAc) 2 ]:[L 1 MgZn(OAc) 2 ]:L 1 Mg 2 (OAc) 2 ]) in line with the elemental analysis results.

The catalyst system obtained in Example 1 a (Catalyst System 1 ) was investigated for its ability to polymerise C0 2 and an epoxide.

2. Polymerisation of carbon dioxide and an epoxide Low Pressure Copolymerization Reactions

Distilled and dried cyclohexene oxide (2.5 mmol, 25 mmol) and the catalyst (0.025 mmol) were placed in a Schlenk tube. The reaction mixture was de-gassed and then heated to 80 °C at 1 bar C0 2 pressure. After a certain reaction time, the mixture was quenched by exposure to air and a 1 H NMR spectrum of the crude mixture was recorded. Then, the cyclohexene oxide was removed, under vacuum, to yield the polycarbonate, which was purified by dissolving it in THF and precipitating it with MeOH.

High Pressure Copolymerization Reactions

The Parr reactor was dried for 20 h at 140 °C and purged with C0 2 three times and allowed to cool to 25 °C. Then, the catalyst (0.03 mmol) dissolved in cyclohexene oxide (15 ml_, 148 mmol) was added to the Parr reactor. After sealing the reactor, 50 bar of C0 2 was added whilst the reaction mixture was stirring at a low-frequency in order to facilitate C0 2 dissolution. This step was repeated several times until the C0 2 dissolution reached equilibrium and the headspace pressure remained constant. The vessel was heated to the appropriate temperature and stirred for a certain time and then a 1 H NMR spectrum of the crude reaction mixture was recorded. The mixture was then taken up in methylene chloride and evaporated to dryness. The white powder polymer was purified by dissolving it in THF and then precipitation with MeOH. a) Polymerisation of an epoxide and carbon dioxide with Catalyst System 1

The activity of Catalyst System 1 for the copolymerization of cyclohexene oxide and carbon dioxide was evaluated using 0.1 mol% of catalyst (vs. epoxide, assuming a 1 :2:1 composition), 1 bar pressure of C0 2 , at 80 °C and over a 6 hour run, as these conditions had previously proved most effective for A. Catalyst system 1 was compared with the two homodinuclear catalysts (A, B) and with the equimolar mixture (1 :1 molar ratio of compounds A:B). The results are shown in Table 1 .

Table 1 : Shows the catalytic activity, productivity, selectivity and molecular weight data for runs using catalysts A and B, and Catalyst System 1. Catalyst TON a) TOF ) % Μ η 0) PDI d)

(h- 1 ) C0 2 c) (g/mol)

A (LZn 2 (OAc) 2 ) 99 ± 1 1 17 ± 2 >99 1300 1.23

B (LMg 2 (OAc) 2 ) 309 ± 34 52 ± 5 >99 5600 1.04

Catalyst System 1 476 ± 31 79 ± 5 >99 5200 1.12

50:50; A:B 239 ± 36 40 ± 6 >99 2900 1 .18

All copolymerizations were conducted in a Schlenk tube at 0.1 % catalyst loading (vs. CHO), 80 °C, 1 bar C0 2 for 6 h. a) The turn over number (TON) = number of moles of cyclohexene oxide consumed/number of moles of catalyst, b) The turn over frequency (TOF) = TON/6, c) Expressed as the percentage carbon dioxide uptake vs the theoretical maximum (100%). This is determined by comparing the relative integrals of the 1 H NMR resonances due to carbonate (δ: 4.65 ppm) and ether (δ: 3.45 ppm) linkages in the polymer backbone, d) Determined by SEC, in THF, using narrow M n polystyrene standards as the calibrant.

Catalyst System 1 is clearly significantly more active than either catalyst A or B; indeed, it has nearly twice the activity of catalyst B, which is itself a notably high activity catalyst. Furthermore, it shows considerably higher activity than the equimolar mixture of catalysts A and B. The equimolar mixture has productivity (TON) and activity (TOF) values that closely match those expected on the basis of the mixture composition: i.e TON mix t ure = (TON ! + TON 2 )/2. This is in line with the mass spectrometry studies that indicated there was no substantial metal exchange between the two catalysts. In contrast, Catalyst System 1 exerts significantly greater activity than the sum of its parts. Catalyst system 1 shows excellent selectivity, with near theoretical uptake of carbon dioxide into the polymer backbone and a very low quantity of ether linkages in the resulting polymer (Table 1 , Figure 16). All the catalysts yield low M n polycarbonates (M n < 6000 g/mol), due to efficient chain transfer reactions with protic impurities (alcohols); see, A. Cyriac, et al, Macromolecules, 2010, 43, 7398-7401 , F. Jutz, et al, J. Am. Chem. Soc, 201 1 , 133, 17395-17405; W. J. van Meerendonk, et al, Macromolecules, 2005, 38, 7306- 7313. Such M n values are highly desirable for the target application as polyols for higher polymer synthesis. Furthermore, using Catalyst System 1 the polydispersity index of the resulting polycarbonate is narrow, indicative of a high degree of polymerization control. The MALDI-ToF spectrum shows two series of chains, both with >99% carbonate linkages, and differing according to the chain end groups: one series is oacetyl-ω- hydroxyl and the other is α,ω-di-hydroxyl end-capped polycyclohexene carbonate (Figure 17).

In order to better understand and compare the activity of Catalyst System 1 with other known epoxide/C0 2 catalysts, experiments were conducted under a range of conditions; see Table 2.

Table 2: Catalytic activity, productivity, selectivity and molecular weight data for experiments using Catalyst System 1.

a) The turn over number (TON) = number of moles of cyclohexene oxide

consumed/number of moles of catalyst, b) The turn over frequency (TOF) = TON/reaction period, c) Expressed as the percentage carbon dioxide uptake vs the theoretical maximum (100%). This is determined by comparing the relative integrals of the 1 H NMR resonances due to carbonate (δ: 4.65 ppm) and ether (δ: 3.45 ppm) linkages in the polymer backbone, d) Determined by SEC, in THF, using narrow M n polystyrene standards. Co salen, Ref C Di-Mg Catalyst, Ref D

Under all conditions, Catalyst System 1 shows very high degrees of polymerization control, as evidenced by the linear increases in molecular weight with the decreasing catalyst concentration. Furthermore, there is no difference in activity, at a fixed catalyst concentration, by changing the C0 2 pressure which is consistent with the earlier finding, using a zinc catalyst, that the rate is independent of its pressure (F. Jutz, ef al, J. Am. C em. Soc, 201 1 , 133, 17395-17405). On the other hand, as expected increasing the temperature significantly improves the activity, whilst maintaining a very high selectivity for carbonate linkages. Compared to some of the best other catalysts for CHO/C0 2 copolymerization, this new system displays excellent activity, selectivity and productivity. For example, it displays equivalent or higher productivities and activities to one of the most active cobalt catalysts (W.-M. Ren, ef a/, Macromolecules, 2010, 43, 1396-1402). Furthermore, compared to one of the few other examples of a di-Mg catalyst, it is 2.5 times faster whilst operating at 5 times lower loading (Y. L. Xiao, ef a/, Macromolecules, 2006, 39, 128-137).

The poly(cyclohexene carbonate) (PCHC) shows monomodal molecular weight distributions and narrow polydisperity indices. This is surprising given that there are three different catalysts present in the mixture. However, it is proposed that the rapid rate of chain transfer, vs. propagation, leads to the narrow distribution in chain lengths and rapid interconversion between all chains with all the catalysts present (S. Inoue, J. Polym. Sci, Part A: Polym. Chem., 2000, 38, 2861-2871 ). This finding is particularly important as it illustrates the potential for such mixed catalyst systems in C0 2 /epoxide copolymerization. Our approach highlights the potential to substantially improve catalyst activity via such a mixed systems approach. Thus, using the Catalyst System 1 allows for an excellent quality of the copolymer formed in terms of molecular weight/PDI.

Reactions were carried out to determine the activity and stability of Catalyst System 1 in the presence of water; see table 3.

Table 3: CHO/C0 2 Copolymerization data for Catalyst System 1 with 16 eq. of H 2 0.

All copolymerizations carried out at in a Schlenk tube for 4h at 80 °C and 1 bar C0 2 , at a 1 :1000 CHO:catalyst loading. a The turn over number (TON) = number of moles of cyclohexene oxide consumed/number of moles of catalyst. b The turn over frequency (TOF) = TON/reaction period. c Determined by the relative integrals of the signals at 3.45 ppm (ether linkages) and 4.65 ppm (polycarbonate) d Determined by SEC in THF, using narrow M n polystyrene standards. It is important that Catalyst System 1 retains its high activity even when 16 equivalents of H 2 0 (vs. catalyst) are added to the reaction (Table 3). This remarkable tolerance to water is highly advantageous, particularly as it obviates complex and difficult drying of epoxides and C0 2 whilst at the same time improving the selectivity for the desired polyol product. The addition of protic reagents, such as water, results in chain transfer via the formation of cyclohexane diol from which telechelic dihydroxyl terminated polymers are produced (F. Jutz, et al, J. Am. Chem. Soc, 201 1 , 133, 17395-17405). Thus, when 16 equivalents of water are added to polymerizations catalysed by Catalyst System 1 , the M n of

polycarbonate reduces to 1300 g/mol, whilst the PDI remains narrow (1.14). Importantly, the α,ω-di-hydroxyl end-capped PCHC chains are produced as the major product, with almost complete suppression of the mono-hydroxyl terminated chains (Figure 18). This selectivity for di-hydroxyl terminated chains is important as such 'polyols' are key reagents for the manufacture of polyurethanes/polyesters. b) Polymerisation of an epoxide and carbon dioxide with other Catalyst Systems

i) Copolymerisation of Cyclohexene Oxide/C0 2 with Catalyst System 7 and [^MgZnBrJ

Table 4: CHO/C0 2 Copolymerisation data for Catalyst System 7 (-65% [L 1 MgZnBr 2 ]), [L 1 MgZnBr 2 ] (>95%) and corresponding homo-bimetallic catalysts

All copolymerizations carried out al in a Schlenk tu oe at 80 °C and 1 bar C0 2 , at a 1 :1000

CHO:catalyst loading. ii) Copolymerisation of Cyclohexene oxide/C0 2 for Catalyst System 2, purified

[L 4 ZnMg(OAc)2] and corresponding homo-bimetallic catalysts

Table 5: CHO/C0 2 Copolymerisation data for Catalyst System 2 and corresponding homo- bimetallic catalysts

1 :1000 CHO:catalyst loading.

Hi) Copolymerisation of Cyclohexene oxide/C0 2 for Catalyst system 6 and corresponding homo-bimetallic catalyst

Table 6: CHO/C0 2 Copolymerisation data for Catalyst System 6 and related homo- bimetallic catalyst

All copolymerisations carried out in a Schlenk tube at 80 °C and 1 bar C0 2 , at loading of 1 :1000 CHO:catalyst. iv) Copolymerisation of Cyclohexene oxide/C0 2 for Catalyst system 5 and corresponding homo-bimetallic catalyst

Table 7: CHO/C0 2 Copolymerisation data for Catalyst System 5 and related homo- bimetallic catalyst

All copolymerisations carried out in a Schlenk tube at 100 °C and 1 bar C0 2 , at loading of 1 :1000 CHO:catalyst. v) Copolymerisation of Cyclohexene oxide/C0 2 for Catalyst system 14

Table 8: CHO/C0 2 Copolymerisation data for Catalyst System 14

All copolymerisations carried out in a Schlenk tube at 80 °C and 1 bar C0 2 , at loading of 1 :1000 CHO:catalyst.

Tables 4 and 5 compare the catalytic activity of homo-bimetallic complexes and their corresponding hetero-bimetallic Catalyst Systems, as well as the high purity hetero- bimetallic complexes. It can be clearly observed from Table 4 that the mixed Catalyst System 7 (which contains -65% [L 1 MgZnBr 2 ] by 1 H NMR) shows similar activity to the homo-bimetallic Mg complex [L 1 MgZnBr 2 ] and significantly greater activity than the di-zinc analogue. The high purity hetero-bimetallic [L 1 MgZnBr 2 ] shows a significantly greater activity than Catalyst System 7 and either of the homo-bimetallic complexes. Table 5 demonstrates that the mixed Catalyst System 2 (already containing a significant amount of the hetero-bimetallic complex [L 4 ZnMg(OAc) 2 ]) shows a much increased activity when compared to the two homo-bimetallic species based on the same ligand structure. The purified hetero-bimetallic compound [L 4 ZnMg(OAc) 2 ] shows even greater activity, demonstrating the surprising activity of the hetero-bimetallic systems in comparison to their homo-metallic analogues and the Catalyst Mixtures containing the homo-bimetallic compounds. Tables 6 and 7 demonstrate the increased activity of the hetero-bimetallic catalyst systems in comparison to one of the corresponding homo-bimetallic catalysts. Table 8 demonstrates the catalytic activity of Catalyst System 14 with and without an added chain transfer agent (iso-propanol). vi) Copolymerisation of Cyclohexene oxide/C0 2 for other metals

Table 9: CHO/C0 2 Copolymerisation data for Catalyst Systems containing other metals

All copolymerisations carried out in a Schlenk tube at 80 °C and 1 bar C0 2 , at loading of

1 :1000 CHO:catalyst.

Table 9 demonstrates the catalyst activity of further catalyst systems 9, 10, 12 and 13 which contain other mixed metal systems (Zn/Co and Zn/Fe). All the systems are active catalysts.