CATALYSTS IN OLEFIN CROSS METATHESIS

Description

The invention relates to immobilized molybdenum and tungsten catalysts. Said catalysts may be used in olefin cross metathesis.

Due to the growing importance of olefin cross metathesis between two different olefins, e.g. ethenolysis of an olefin, a great need exists for the provision of appropriate methods which can be beneficially carried out at an industrial scale. In particular, the manufacture of propylene starting from 2-butene and ethylene is of particular importance due to the growing importance of propylene as starting material for many industrial processes. US 2012/0316057 relates to a tungsten catalyst comprising a tungsten metal compound which contains a least one tungsten-fluorine bond, the compound being dispersed on a refractory oxide support, wherein the compound is chemically bonded to the support. Said catalyst may be employed in the metathesis reaction of 2-butene and ethylene to produce propylene.

N. Rendon et. al., Chem. Eur. J. 2009, 15, 5083-5089, disclose silica supported Mo- alkylidene catalysts containing one OR substituent which may be used in olefin metathesis reactions. F. Blanc et al., J. Amer. Chem. Soc. 2007, 129, 8434-8435, disclose silica supported Mo- alkylidene catalysts containing a pyrrolide substituent which can be used in an olefin metathesis reaction.

One object to be achieved by the present invention is the provision of a method for per- forming cross metathesis between two different olefins which beneficially can be carried out at an industrial scale. This object is achieved with a method in which the metathesis between two different olefins is catalyzed by means of immobilized molybdenum-alkylidene or tungsten-alkylidene catalysts. Contrary to homogeneous catalysis, where the catalyst frequently has to be separated off by a rather complex processing of the reaction mixture, whereby the cata- lyst often is destroyed or at least considerably deteriorated in its activity, the catalysts employed in the process according to the invention may be separated off from the reaction mixture via simple processing, e.g. by filtration or centrifugation. The catalysts may be re-used in olefin metathesis. This is particularly beneficial at an industrial scale. The method according to the invention differs from the known use of silica supported Mo- alkylidene catalysts containing one OR substituent. This prior art discloses heterogene- ously catalyzed olefin homo or self metathesis (SM) and ring closing metathesis (RCM) (N. Rendon et. al., Chem. Eur. J. 2009, 15, 5083-5089) whereas the subject method relates to a cross metathesis reaction between two different olefins. The method according to the invention also differs from the known use of Mo-alkylidene catalysts containing a pyrrolide substituent. This prior art discloses self metathesis (SM) of propene (F. Blanc et al., J. Amer. Chem. Soc. 2007, 129, 8434-8435) whereas the subject method relates to a cross metathesis reaction between two different olefins. Since the structure of the catalysts used in the present invention has an alkylidene group and the structure of the cata- lysts disclosed in US 2012/0316057 is free of an alkylidene group, said catalysts are different from one another.

In a first aspect, the invention relates to a method of forming an olefin from a first olefin and a second olefin in a metathesis reaction, comprising at least step (i):

(i) reacting the first olefin with the second olefin in the presence of a silica supported Mo-alkylidene or W-alkylidene catalyst, wherein the first olefin and the second olefin are different from one another.

Preferably, the method according to step (i) is carried out in a solvent, which dissolves the olefins and suspends the catalyst. Suitable solvents are solvents selected from aro- matics, preferably toluene, halogenated solvents, preferably chlorobenzene or methylene dichloride, alkanes, preferably pentane or hexane or octane. However, step (i) may be carried out without solvent, preferably if one of the olefins is a liquid under the reaction conditions. However, the reaction may also be carried out such that the first olefin and the second olefin are in gaseous phase or the first olefin is gaseous and the second ole- fin is in liquid phase..

The temperature employed in step (i) preferably ranges from - 20 °C to 200 °C, more preferably from 0 °C to 110 °C, still more preferably from 15 to 50 °C. The concentration of the catalyst can vary in broad ranges. Preferably, the catalyst is employed in a molar ratio of < 5 mole % (calculated in terms of W or Mo), based on the first or the second olefin (100 mole %).

The cross metathesis (CM) between the first and the second olefin may be carried out with various types of olefins.

Preferably,

(a) the first olefin is a cyclic olefin and the second olefin is a cyclic olefin; or

(b) the first olefin is a cyclic olefin and the second olefin is a non-cyclic olefin; or (c) the first olefin is a non-cyclic olefin and the second olefin is a non-cyclic olefin.

Preferably, the first olefin or the second olefin is a C - C ₃₀ olefin. The inventors of the present invention have discovered that the method according to the invention may be particularly advantageously employed as ethenolysis. Accordingly, the first olefin and the second olefin are a C ₄ - C ₃₀ olefin and ethylene.

Thus, in a preferred embodiment, the first olefin has an internal olefinic double bond and the second olefin is ethylene. The olefin subjected to ethenolysis may be a cyclic or a non-cyclic olefin. Most preferably, the first olefin is 2-butene and the second olefin is ethylene. Thus, the method according to the invention can be used for the manufacture of propylene using 2-butene and ethylene as starting materials. The proceeding of the reaction may be preferably controlled by gas chromatographic methods.

Preferably, the reaction is terminated by separating off the catalyst from the reaction mixture obtained in step (i). Preferably, separating off may be performed by methods such as filtration or centrifugation or by distilling olefin off. The thus recovered catalyst may be re-used in step (i).

Accordingly, in one embodiment, the method according to the invention further comprises at least step (ii) or step (ii) and step (iii):

(ii) separating off the catalyst from the reaction mixture obtained in step (i), preferably by filtration or centrifugation;

(iii) re-using in step (i) the catalyst obtained in step (ii). The silica-supported Mo- and W-alkylidene catalysts which can be employed in the method according to the invention are either known or may be prepared according to known methods, e.g. according to the method as described above in N. Rendon et. al., Chem. Eur. J. 2009, 15, 5083-5089. Preferably, the catalyst used in the reaction according to the invention is of formula I wherein

M is W or Mo;

R ¹ is H, aryl, heteroaryl, alkyl, or heteroalkyi, optionally substituted, respectively;

R ² and R ³ can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyi, het- eroalkenyl, aryl, or heteroaryl, optionally substituted, respectively;

R ⁵ is a residue R ⁶ -X-, wherein

R ⁶ is alkyl, aryl, heteroalkyi, or heteroaryl, optionally substituted, respectively;

(R ⁷ , R ⁸ , R ⁹ )Si, wherein R ⁷ , R ⁸ , R ⁹ are independently alkyl, alkoxy, phenyl or phenoxy, optionally substituted, respectively; (R ⁰ , R ¹¹ , R ¹² )C, wherein R ¹⁰ , R ¹¹ , R ¹² are independently phenyl or alkyl, optionally substituted, respectively;

X = O, S, or NR ¹³ , wherein R ¹³ is H; or alkyl or aryl, optionally substituted, respectively; or

R ⁵ is R ⁶ -CO-NR ¹³ , wherein R ⁶ and NR ¹³ have the meaning as defined above, or wherein R ⁶ and R ³ taken together form a carbon chain having from 2 to 6 carbon atoms;

R ⁵ is a 4 to 8 membered N-containing ring, preferably a carbon ring, wherein N is linked to M; and

R ⁴ is a residue 0-Si(0-) ₃ , and represents silica to which M is linked forming a M-0-Si(0- )3 moiety, preferably wherein silica is comprised in a solid support. In one embodiment, a catalyst of formula I is provided in which R ¹ is aryl or adamant-1-yl, optionally substituted, respectively; preferably wherein R is phenyl or naphthyl, or phenyl or naphthyl substituted with up to five substituents independently selected from C C alkyl, C ₁ -C ₄ alkoxy, CF ₃ , F, CI, Br, or phenyl or phenoxy, optionally substituted, respectively;

R ² is -C(CH ₃ ) ₂ C ₆ H ₅ or -C(CH ₃ ) ₃ ;

R ³ is H;

R ⁵ is a residue R ⁶ -X-, wherein

X = O and R ⁶ is phenyl or phenyl substituted with up to five substituents independently selected from alkyl, preferably C -C alkyl, such as methyl, isopropyl or t-butyl; alkoxy, preferably C C alkoxy; phenoxy, phenyl, optionally substituted, respectively; or halogen; or

X = S and R ⁶ is phenyl substituted with up to five substituents independently selected from alkyl, preferably C^C^ alkyl such as methyl, isopropyl or t-butyl; alkoxy, preferably C1-C4 alkoxy; phenoxy, phenyl, optionally substituted, respectively; or halogen; or X = O and R ⁶ is triphenylsilyl or triphenoxysilyl, optionally substituted, respectively; or tri(C C ₄ alkyhsilyl or tri(C C alkoxy)silyl;

X = O and R ⁶ is triphenylmethyl, optionally substituted; or

X = O and R ⁶ is 9-phenyl-fluorene-9-yl; or

X = O and R ⁶ is 2-phenyl-1 ,1 ,1 ,3,3,3-hexafluoro-prop-2-yl [(C ₆ H ₅ )(CF ₃ )2C]; or

X = O and R ⁶ is t-butyl, optionally substituted with one or more F groups, preferably (CF ₃ )(CH ₃ ) ₂ C, (CF ₃ ) ₂ (CH ₃ )C, (CF ₃ ) ₃ C.

In a preferred embodiment, R is -C(CH ₃ ) ₂ C ₆ H ₅ . In another embodiment, a catalyst of formula I is provided in which

R ¹ is phenyl substituted with up to five substituents independently selected from C C ₄ alkyl, C C ₄ alkoxy, CF ₃ , F, CI, Br, or phenyl or phenoxy, optionally substituted, respectively; and

X = O and R ⁶ is phenyl or phenyl substituted with up to five substituents independently selected from C1-C4 alkyl, C1-C4 alkoxy, phenoxy, phenyl, halogen; or

X = S and R ⁶ is phenyl or phenyl substituted with up to five substituents independently selected from C C ₄ alkyl, C C alkoxy, phenoxy, phenyl, halogen; or X = O and R ⁶ is triphenylsilyl, triphenoxysilyl, tri(Ci-C ₄ alkyl)silyl or tri(C -C ₄ alkoxy)silyl; or

X = O and R ⁶ is t-butyl or t-butyl substituted with one or more F groups, preferably (CF ₃ )(CH ₃ ) ₂ C, (CF ₃ )2(CH3)C, (CF ₃ ) ₃ C; or (C ₆ H ₅ )(CF ₃ ) ₂ C; or

R ⁵ is pyrrol-1-yl, 2,5-dimethylpyrrol-1-yl, or 2,5-diphenylpyrrol-1-yl.

The inventors of the present invention have surprisingly discovered that the efficacy of the catalyst used in the method according to the invention may be further enhanced by a purposive selection of the residues R ¹ and R ⁵ .

Accordingly, in one preferred embodiment, a catalyst of formula I is provided in the method according to the invention in which R ¹ is an electron donating group and R ⁵ is an electron withdrawing group. Preferably, a catalyst is provided in which

R ¹ is phenyl substituted with up to five substituents independently selected from alkyl, C-1-C4 alkoxy, phenyl, phenoxy;

R ² is -C(CH ₃ ) ₂ C ₆ H5 or -C(CH ₃ ) ₃ ;

R ³ is H;

R ⁵ is (CF ₃ )(CH ₃ ) ₂ CO, (CF ₃ ) ₂ (CH ₃ )CO, (CF ₃ ) ₃ CO, (C ₆ H ₅ )(CF ₃ ) ₂ CO, pyrrol-1-yl, 2,5- dimethylpyrrol-1-yl, or 2,5-diphenylpyrrol-1-yl.

Preferably, R ¹ is 2,6-diisopropylphenyl. The inventors have further discovered that the object is also achieved if R ¹ is an electron withdrawing group and R ⁵ is an electron donating group.

Preferably, a catalyst of formula I is provided in which

R ¹ is phenyl substituted with up to five substituents independently selected from CF ₃ , F, CI, Br;

R ² is -C(CH ₃ ) ₂ C ₆ H ₅ or -C(CH ₃ ) ₃ ;

R ³ is H; R ⁵ is (CH ₃ ) ₃ CO, tri(C ₁ -C ₄ )silyloxy, or tri(phenyl)silyloxy; or phenoxy or phenylthio, wherein the phenyl moiety may be substituted with up to five substituents independently selected from C C ₄ alkyl, C C ₄ alkoxy, phenoxy, phenyl, halogen. Preferably, R ¹ is 2,6-dichlorophenyl, pentafluorophenyl, 2-(trifluoromethyl)phenyl or 2,6- di(trifluoromethyl)phenyl.

Catalysts in which both R ¹ and R ⁵ are electron withdrawing groups may also be used in the method according to the invention.

Compounds in which both R ¹ and R ⁵ are electron withdrawing groups preferably may have a structure in which

R ¹ is phenyl substituted with up to five substituents independently selected from CF ₃ , F, CI, Br;

R ² is -C(CH ₃ ) ₂ C ₆ H ₅ or -C(CH ₃ ) ₃ ;

R ³ is H;

R ⁵ is (CF ₃ )(CH ₃ ) ₂ CO, (CF ₃ )2(CH3)CO, (CF ₃ ) ₃ CO, (C ₆ H ₅ )(CF ₃ ) ₂ CO, pyrrol-1-yl, 2,5- dimethylpyrrol-1-yl, or 2,5-diphenylpyrrol-1-yl. Preferably, R ¹ is 2,6-dichlorophenyl, pentafluorophenyl, 2-(trifluoromethyl)phenyl or 2,6- di(trifluoromethyl)phenyl.

The compounds of formula I used in the method according to the invention may be prepared by grafting appropriate precursor compounds on silica or on a support comprising silica.

Preferably, a silca is used which is partially dehydrated or dehydroxylated.

Preferably, silica is dehydroxylated and dehydrated at elevated temperature, preferably at elevated temperature and in vacuo. Preferably, silica is dehydroxylated and dehydrated at 700 °C (Si0 _2- (7oo))- However, other temperaturesor temperture ranges may also be used depending on the requirements of the compound of formula I to be used as heterogeneous catalyst. Suitable precursor compounds are e.g. compounds of formula I in which R ⁴ is a ligand that can be replaced by a 0-Si(0-) ₃ moiety. Suitable ligands are preferably alkoxy and 2,5-dimethylpyrrol-1-yl ligands. Suitable precursor compounds are known or may be prepared according to known methods. According to a second aspect, the invention relates to the use of a silica supported Moor W-alkylidene catalyst as defined in the first aspect in an olefin cross metathesis between a first olefin and a second olefin, wherein the first and the second olefin are different from one another. Preferably, said cross metathesis reaction is ethenolysis.

Definitions as used in the meaning of the invention

The catalyst according to the invention is heterogeneous, i.e. it comprises a solid sup- port. Said solid support comprises silica or consists of "silica".

A solid support may be any material that includes silica such as silica as such or silica in combination with other materials. Accordingly, silica may be used in the form of a mixed oxide, e.g. a mixed oxide of silica and alumina or silica and zirconia. Preferably, silica is used as such as solid support.

The term "silica" further encompasses porous or non-porous silica.

The term further encompasses partially dehydroxylated and/or dehydrated silica. Dehy- droxylation and/or dehydration may be performed using elevated temperature or elevat- ed temperature and vacuum. Residual hydroxyl content may be determined by titration with MeMgCI. Hydroxyl content may be freely selected depending on drying temperature and drying time. Accordingly, the silica used for the compounds according to the invention may be adjusted in a tailor-made manner to the required properties of the W-compound to be immobilized. In this regard it is noteworthy that depending on the number of mmol of hy- droxyl groups per gram silica, the amount of W compound per gram of silica and ultimately the activity of the resulting catalyst may be adjusted depending upon needs.

In a preferred embodiment, silica is subjected to a temperature in the range of from 400 to 800 °C for a period ranging from 4 to 24 under pressure ranging from 10 ^~6 mbar to 1 bar. Temperature and pressure may be performed in ramps.

Preferably, hydroxyl content determined by means of titration with MeMgCI ranges from 0.05 mmol to 2.00 mmol per g silica, further preferred from 0.1 mmol to 1 mmol per g silica.

The term "metathesis" refers to alkene (olefin) metathesis.

The term "cross metathesis" encompasses the reaction between two different olefins. The term "ethenolysis" encompasses the reaction of an olefin having an internal olefinic bond with ethylene.

The term "turnover frequency (TOF)" defines the number of turnovers of moles of olefin per time unit of a certain catalyst. The term "electron withdrawing" or "electron withdrawing group (EWG)" encompasses a group which draws electrons away from the central W of the compound according to the invention.

The term "electron donating group" or "electron donor" encompasses a group which do- nates electrons to the central W of the compound according to the invention. The person skilled in the art is familiar with terms such as "electron withdrawing group (EWG)" or "electron donor" and can residues R ¹ and R ⁵ attribute to the respective properties. The term "olefinic double bond' refers to a carbon-carbon double bond or ethylenic double bond in a first olefin and a second olefin.

The term "olefin" as used in the terms "first olefin" and "second olefin" refers to any species having at least one ethylenic double bond such as linear and branched chain ali- phatic olefins, cycloaliphatic olefins, or aryl substituted olefins. Olefins may comprise terminal double bond(s) ("terminal olefin") and/or internal double bond(s) ("internal olefin") and can be cyclic or acyclic, linear or branched, optionally substituted. The total number of carbon atoms can be from 2 to 100, or from 2 to 40; the double bonds of a terminal olefin may be mono- or bi-substituted and the double bond of an internal olefin may be bi-, tri-, or tetrasubstituted. In some cases, an internal olefin is bisubstituted.

Non-limiting examples of terminal olefins are substituted and unsubstituted linear alkyl internal olefins such as C ₄ -C ₃ o olefins (e.g., 1-butene, 1 -pentene, 1-hexene, 1-heptene, 1-octene, -decene, 1 -dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1- eicosene, allylbenzene, allyltrimethylsilane, methyl-10-undecenoate, allylboronic acid pincol ester, allylbenzylether, N-allyl-4-methylbenzenesulfonamide, allylaniline, methyl-9- decenoate, allyloxy(tert-butyl)dimethyl silane, allylcyclohexane, etc.).

In one embodiment, the olefin having a terminal olefinic double bond is of formula RCH=CH ₂ , wherein R is selected from H, alkyl, alkenyl, aryl, heteroalkyl, heteroalkenyl, heteroaryl, or acyl, optionally substituted.

In one embodiment, the olefin is a polyisoprene. The term "cyclic olefin" refers to any cyclic species comprising at least one ethylenic double bond in a ring. The atoms of the ring may be optionally substituted. The ring may comprise any number of carbon atoms and/or heteroatoms. In some cases, the cyclic olefin may comprise more than one ring. A ring may comprise at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, or more, atoms. Non-limiting examples of cyclic olefins include norbornene, dicyclopentadiene, bicyclo compounds, oxabicyclo compounds, and the like, all optionally substituted. "Bicyclo compounds" are a class of compounds consisting of two rings only, having two or more atoms in common. "Oxabicyclo compounds" are a class of compounds consisting of two rings only, having two or more atoms in common, wherein at least one ring comprises an oxygen atom.

In another embodiment, the first and the second olefin or the first and the second olefin may bear one or more functional groups.

Preferably, the first and the second olefin or the first or the second olefin may bear one or more functional groups independently selected from the group consisting of ether, ester, amide, amine, halogen, nitrile, thioether, thioester, aryl, or heteroaryl. In a further preferred embodiment, the first and the second olefin or the first or the second olefin bear one or more functional groups independently selected from alkoxy, ar- yloxy, perhaloalkoxy, arylalkoxy, heteroaryl, heteroaryloxy, heteroarylalkyl, het- eroarylalkoxy, amino, halogen, alkylthio, oxo, carboxy esters, carboxamido, acyloxy, aminoalkyl, alkylaminoaryl, alkylaminoalkyl, alkoxyaryl, arylamino, arylalkylamino, alkyl- sulfonyl, carboxamidoalkylaryl, carboxamidoaryl, hydroxyalkyl, haloalkyl, alkylaminoal- kylcarboxy-, aminocarboxamidoalkyl-, cyano, alkoxyalkyl, perhaloalkyl, arylalkyloxyalkyl.

The term "alkyf encompasses saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl substituted cy- cloalkyl groups, and cycloalkyl substituted alkyl groups and alkyl groups substituted with aryl. In certain embodiments, a straight chain or branched chain alkyl has about 30 or fewer carbon atoms in its backbone (e.g., C-1-C30 for straight chain, C ₃ -C ₃₀ for branched chain), and alternatively, about 20 or fewer. Likewise, cycloalkyls have from about 3 to about 10 carbon atoms in their ring structure, and alternatively about 5, 6 or 7 carbons in the ring structure. In some embodiments, an alkyl group may be a lower alkyl group, wherein a lower alkyl group comprises 10 or fewer carbon atoms in its backbone (e.g., C do for straight chain lower alkyls). ln one embodiment, the term "alkyf encompasses C^-C ₄ alkyl such as methyl, isopropyl iPr) or t-butyl (tBu).

The term "alkyf also encompasses bridged hydrocarbon residues such as the adamantyl residue, particularly the adamant-1-yl residue.

The term "alkyf also encompasses anellated ring systems such as the fluorene-9-yl residue such as the 9-phenyl-fluorene-9-yl residue. The term "t-Bu" denotes a tertiary butyl group (CH ₃ ) ₃ C.

The term "tBu _F 3 denotes a tertiary butyl group (CF ₃ )(CH ₃ ) ₂ C. The term "tBu _F e denotes a tertiary butyl group (CF ₃ ) ₂ (CH ₃ )C. The term "tBu _F9 " denotes a tertiary butyl group

(CF ₃ ) ₃ C.

The term "alkoxy" refers to the group -O-alkyl, wherein alkyl has the meaning as defined above in connection with the term alkyl.

The term "alkenyr refers to olefinic groups as described above. The alkenyl group may be optionally substituted with the substituents defined above.

The term "aryP' refers to aromatic carbocyclic groups, optionally substituted, having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple fused rings in which at least one is aromatic (e.g., 1 ,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl). That is, at least one ring may have a conjugated κ electron system, while other, adjoining rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, and/or heterocyclyls. The aryl group may be optionally substituted, as described herein.

The term "carbocyclic aryl groups" as used herein refers to aryl groups wherein the ring atoms on the aromatic ring are carbon atoms. Carbocyclic aryl groups include monocyclic carbocyclic aryl groups and polycyclic or fused compounds (e.g., two or more adjacent ring atoms are common to two adjoining rings) such as naphthyl groups. In some cases, the aryl groups may include monocyclic carbocyclic aryl groups and polycyclic or fused compounds (e.g., two or more adjacent ring atoms are common to two adjoining rings) such as naphthyl group. Non-limiting examples of aryl groups include phenyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, and the like.

A preferred aryl residue is 2,6-diisopropylphenyl as residue R ¹ . A further preferred aryl residue is 2,6-dichlorophenyl as residue R ¹ or pentafluorophenyl, 2- (trifluoromethyl)phenyl or 2,6-di(trifluoromethyl)phenyl.

The term "phenoxy" refers to the group C ₆ H ₅ 0 -.

The term "thiophenoxy" or "phenylthio" refers to the group C ₆ H ₅ S -

This phenoxy or thiophenoxy residue may be substituted with up to five substituents independently selected from alkyi, preferably C C ₄ alkyi such as methyl, isopropyl or t- butyl, alkoxy, preferably C- -C ₄ alkoxy, phenoxy, phenyl, halogen.

A preferred phenoxy residue is 2,6-diphenylphenoxy as residue R ⁵ or 4-fluoro-2,6- dimesitylphenoxy or 2,6-di-tert.-butylphenoxy 4-bromo-2,6-di-tert.-butylphenoxy or 4- methoxy-2,6-di-tert.-butylphenoxy or 4-methyl-2,6-di-tert.-butylphenoxy or 2,4,6-tri-tert.- butylphenoxy or 2,3,5,6-tetraphenylphenoxy or 4-bromo-2,3,5,6-tetraphenylphenoxy or 2,6-di(4-bromophenyl)-3,5-diphenylphenoxy or 4-bromo-2,6-di(4-bromophenyl)-3,5- diphenylphenoxy.

A preferred thiophenoxy residue is 2,6-diphenylthiophenoxy, 4-bromo-2,6- diphenylthiophenoxy, 4-fluoro-2,6-diphenylthiophenoxy, 4-methyl-2,6- diphenylthiophenoxy, 2,4,6-triphenylthiophenoxy, 4-fluoro-dimesitylthiophenoxy, 2,6-di- tert.-butylthiophenoxy, 4-bromo-2,6-di-tert.-butylthiophenoxy, 4-methoxy-2,6-di-tert.- butylthiophenoxy, 4-methyl-2,6-di-tert.-butylthiophenoxy, 2,4,6-tri-tert.-butylthiophenoxy, 2,3,5,6-tetraphenylthiophenoxy, 4-bromo-2,3,5,6-tetraphenylthiophenoxy, 2,6-di(4- bromophenyl)-3,5-diphenylthiophenoxy, 4-bromo-2,6-di(4-bromophenyl)-3,5- diphenylthiophenoxy as residue R ⁵ . The term "heteroaryf as used herein refers to aryl groups as described herein in which one or more atoms is a heteroatom (e.g., oxygen, nitrogen, sulfur, and the like), optionally substituted. Examples of aryl and heteroaryl groups include, but are not limited to, phenyl, aryloxy, pyrrolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, thiazolyl, triazolyl, pyra- zolyl, pyridinyl, pyrazinyl, pyridazinyl and pyrimidinyl, and the like.

A preferred heteroaryl residue as residue R ⁵ is the pyrrol-1 -yl residue (py) or 2,5- dimethylpyrrol-1-yl (2,5-Me ₂ py or Me ₂ pyr) or 2,5-diphenylpyrrol-1-yl. The pyrrol-1 -moiety is also termed as pyrrolide.

The term "heteroalkyr refers to alkyl groups as described herein in which one or more atoms is a heteroatom (e.g., oxygen, nitrogen, sulfur, and the like). Examples of het- eroalkyl groups include, but are not limited to, alkoxy, poly(ethylene glycol)-, alkyl- substituted amino, tetrahydrofuranyl, piperidinyl, morpholinyl, etc.

The term "halogen" refers to F, CI, Br, I.

The term "acyf refers to H, alkyl, alkenyl, aryl, heteroalkyl and heteroaryl groups as defined above, which are linked to another atom or to another moiety such as a olefinic double bond via a carbonyl group.

The term "triphenylsilyloxy" refers to preferred group (C ₆ H ₅ ) ₃ SiO, wherein the phenyl residue may be substituted. The term "triphenoxysilyloxy" refers to group (C ₆ H ₅ 0) ₃ SiO, wherein the phenyl residue may be substituted.

The term "trialkylsilyloxy" refers to preferred group (d _ C ₄ ) ₃ SiO, wherein the alkyl residue may be substituted. The term "trialkoxysilylox refers to group (C-i _ C ₄ 0) ₃ SiO, wherein the alkoxy residue may be substituted. The term "comprising" is used in the meaning of "including but not limited to".

The term "consisting of is used in the meaning "including and limited to". The term "first or second olefin" is in one embodiment synonymously used with the term "first and second olefin".

The term "chemical reaction" encompasses a reaction in which in a compound a new bond is formed.

The terms "substituted' and "optionally substituted' are contemplated to include all permissible substituents of organic compounds, "Permissible" being in the context of the chemical rules of valence known to those of ordinary skill in the art. Examples of substit- uents include, but are not limited to, alkyl, aryl, arylalkyl, cyclic alkyl, heterocycloalkyl, hydroxy, alkoxy, aryloxy, perhaloalkoxy, arylalkoxy, heteroaryl, heteroaryloxy, het- eroarylalkyl, heteroarylaikoxy, azido, amino, halogen, alkylthio, oxo, acylalkyi, carboxy esters, carboxyl, -carboxamido, nitro, acyloxy, aminoalkyl, alkylaminoaryl, alkylaryl, al- kylaminoalkyl, alkoxyaryl, arylamino, arylalkylamino, alkylsulfonyl, -carboxamidoalkylaryl, -carboxamidoaryl, hydroxyalkyl, haloalkyl, alkylaminoalkylcarboxy-, aminocarboxami- doalkyl-, cyano, alkoxyalkyl, perhaloalkyl, arylalkyloxyalkyl.

In one embodiment, the term "R ⁶ -CO-NR ^13" means a 4 to 8 membered cyclic carbon- and N-containing ring in which N is linked to M.

The term "N-containing carbon ring" means that the ring contains besides carbon atoms at least one nitrogen atom.

Examples

1. General procedures

All experiments were carried out under dry and oxygen free argon atmosphere using either standard Schlenk or glove-box techniques for organometallic synthesis. For the syntheses, reactions were carried out using high vacuum lines (10 ^~5 mBar) and glove-box techniques. Pentane, toluene and diethyl ether were purified using double MBraun SPS alumina column, and were degassed using three freeze-pump-thaw cycles before being used. DME and THF were distilled from Na/Benzophenone. Silica (Aerosil Degussa, 200 m ² g ^"1 ) was compacted with distilled water, calcined at 500°C under air for 4 h and treated under vacuum (10 ^~5 mBar) at 500°C for 12 h and then at 700°C for 4 h (support referred to as SiO _2- (700)) and contained 0.26 mmol of OH per g as measured by titration with MeMgCI. All infrared (IR) spectra were recorded using a Bruker spectrometer placed in the glovebox, equipped with OPUS software. A typical experiment consisted in the measurement of transmission in 32 scans in the region from 4000 to 400 cm ^"1 . The ¹ H and ¹³ C-NMR spectra were obtained on Bruker DRX 200, DRX 250 or DRX 500 spectrometers. The solution spectra were recorded in C ₆ D ₆ at room temperature. The ¹ H and ¹³ C chemical shifts are referenced relative to the residual solvent peak. Compounds [W(NAr)(CHCMe ₃ )(OtBu) ₂ ], [W(NAr)(CHCMe ₃ )(OtBu _F3 ) ₂ ], [W(NAr)(CHCMe ₃ )(OtBu _F6 ) ₂ ], ¹ [W(NAr _C i)(CHCMe ₂ Ph)(Me ₂ Pyr) ₂ ], ² [W(NAr _C i)(CHCMe ₃ )(OtBu _F6 ) ₂ ], ² [Mo(NAr _C i)(CHCMe ₂ Ph)(Me ₂ Pyr) ₂ ], ³

[(≡SiO)W(NAr)(CHCMe ₃ )(Me ₂ Pyr)], ⁴ [(=SiO)Mo(NAr)(CHCMe ₃ )(Me ₂ Pyr)], ⁵ and [(≡SiO)Mo(NAr)(CHCMe ₃ )(OtBu _F6 )] ⁶ were synthesized according to literature proce- dures. Further precursors or starting materials may be prepared according to such procedures or according to methods specified in the following.

¹ Schrock, R. R.; De Pue, R. T.; Feldman, J.; Yap, K.B.; Yang, D. C; Davis, W. M.; Park, L; Dimare, M.; Schofield, M.; Anhaus, J.; Walborsky, E.; Evitt, E.; Kriiger, C; Betz, P. Organometallics 1990, 2262. ² Arndt, S.; Schrock, R. R.; Muller, P . Organometallics 2007 ^' , 1279.

³ Schrock, R. R.; Jamieson, J. Y.; Dolman, S. J.; Miller, S. A.; Bonitatebus, P. J., Jr.; Hoveyda, A. H. Organometallics 2002, 21, 409. Blanc, F.; Berthoud, R.; Coperet, C; Lesage, A.; Emsley, L; Singh, R.; Kreickmann, T.; Schrock, R. R. Proc. Nat. Acad. Sci. 2008, 12123.

⁵ Blanc, F.; Thivolle-Cazat, J.; Basset, JM.; Coperet, C. Chem. Eur. J. 2008, 9030.

⁶ Rendon, N.; Berthoud, R.; Blanc, F.; Gajan, D. ; Maishal, T.; Basset, JM.; Coperet, C; Lesage, A.; Emsley, L.; Marinescu, S. C; Singh, R.; Schrock, R. R. Chem. Eur. J. 2009, 5083.

Abbreviations:

THF = tetrahydrofuran

DME = 1 ,2-dimethoxyethane

Et ₂ 0 = diethyl ether

TfOH = trifluoromethanesulfonic acid

LiMe ₂ Pyr =lithium 2,5-dimethylpyrrolide

2. Syntheses

2.1 Synthesis of precursors:

Precursor example 1 : [W(NAr)(CHCMe ₃ )(OtBu _F9 )2], Ar = 2,6-iPr ₂ C ₆ H ₃

A cold (-40 °C) suspension of (CF ₃ ) ₃ COLi (148 mg, 0.61 mmol, 2 equiv.) in diethyl ether (2 mL) was added to a solution of 250 mg of [W(NAr)(CHCMe ₃ )(OTf) ₂ (DME)] (0.305 mmol, 1 .05 equiv.) in cold diethyl ether (6 mL, -40 °C) while stirring. The dark red solution was stirred for 2h at room temperature, and the volatiles were removed under reduced pressure. The dark red solid was suspended in pentane (4 mL) and filtered on Celite® to afford a clear orange solution. The filtrate was taken to dryness in vacuo, and the orange powder dissolved back in pentane (2 mL). This drying/dissolution cycle was repeated four consecutive times, in order to remove all the coordinated DME molecules. Finally, the orange powder was solubilized in a minimum amount of pentane, and stored at -40 °C to give orange crystals, that were washed with cold (-40 °C) pentane, affording after drying in vacuo 218 mg of [W(NAr)(CHCMe ₃ )(OtBu _F 9) ₂ ] (0.21 mmol, 69%). ¹ H NMR (200 MHz, C ₆ H ₆ ) δ (ppm) 9.45 (s, 1 H, CHCMe ₃ ), 7.04-6.94 (m, 3H, Ar), 3.46 (2H, septet, CHMe ₂ ), 1.15 (d, 12H, CHMe ₂ ), 1.06 (s, 9H, CHCMe ₃ ). ¹⁹ F NMR (200 MHz, C ₆ D ₆ ) δ (ppm) -73.1 (s, 18F, C(CF ₃ )).

Precursor example 2: [W(NAr _C i)(CHCMe ₂ Ph)(OtBu _F 9) ₂ (DME)], Ar _C i = 2,6-CI-C ₆ H ₃

A cold (-40 °C) suspension of (CF ₃ ) ₃ COLi (162.4 mg, 0.67 mmol, 2 equiv.) in diethyl ether (4 mL) was added to a suspension of 250 mg of [W(NAr _C i)(CHCMe ₂ Ph)(OTf) ₂ (DME)] (0.33 mmol, 1 equiv.) in cold diethyl ether (6 mL, - 40 °C) while stirring. The dark brown reaction mixture was stirred for 1.5 h at room temperature, and the volatiles were removed under reduced pressure, affording a light brown solid. The solid was extracted in pentane (15 mL), filtered on Celite® and rinsed with pentane (2 x 5 mL). The volume of the filtrate was reduced to ca. 2 mL in vacuo and was stored at -40 °C, affording an orange powder. The powder was filtered and rinsed with cold (-40°C) pentane (2 x 1 mL) to afford after drying in vacuo 165.2 mg of an orange powder of the title compound (0.159 mmol, 48 %). Single crystals suitable diffraction studies of [W(NAr _C i)(CHCMe ₂ Ph)(OtBu _F 9) ₂ ] were grown in -40°C toluene. ¹ H NMR (300 MHz, C ₆ H ₆ ) δ (ppm) 9.61 (s, 1 H, CHCMe ₃ ), 7.45 (m, 2H, Ph), 7.00 (m, 2H, Ph), 6.74 (m, 1 H, Ph), 6.69 (d, 2H, Ar, J = 8.1 Hz), 6.19 (t, 1 H, Ar, J = 8.2 Hz), 3.00 (s, 6H, DME), 2.87 (s, 4H, DME), 1 .44 (s, 6H, CHC e ₂ Ph). ¹⁹ F NMR (300 MHz, C ₆ D ₆ ) δ (ppm) -73.1 (s, 18F, C(CF ₃ )).

Precursor example 3: rW(NAr _C i)(CHCMe ₂ Ph)(OtBu)2], Ar _a = 2,6-CI-C ₆ H ₃

To a cold THF solution (-41 °C, 20 mL) of [W(NAr _C i)(CHCMe ₂ Ph)(Me ₂ Pyr) ₂ ] (200 mg, 0.30 mmol, 1 equiv.) was added dropwise over 1 h a solution of tBuOH (44.6 mg, 0.60 mmol, 2 equiv.) in cold THF (-41 °C, 10 mL). The resulting brown solution was further stirred overnight in the MeCN/C0 ₂ bath, slowly reaching room temperature. The resulting dark brown solution was dried in vacuo (2 h, 10 ^~2 mBar). The brown residue was extract- ed in cold pentane (-40 °C, 3 mL), filtered on Celite® and evaporated to dryness to afford 108 mg of an oily orange solid (0.173 mmol, 57 %). ¹ H NMR (300 MHz, C ₆ H ₆ ) δ (ppm) 8.09 (s, 1 H, CHCMe ₂ Ph), 7.54 (m, 2H, Ph), 7.16 (m, 2H, Ph), 7.08 (m, 1 H, Ph), 6.97 (m, 2H, Ar _C i), 6.31 (t, 1 H, Ar _a , J = 8.2 Hz), 1.72 (s, 6H, CHCMe ₂ Ph), 1.26 (s, 18H, OCMe ₃ ).

Precursor example 4: [W(NAr _C F3)(CHCMe ₂ Ph)(Me2Pyr)23, (Ar _CF 3 = 2-CF ₃ -C ₆ H ₄ , Me ₂ Pyr = 2,5-dimethylpyrrolide)

A cold suspension of 47.5 mg of LiMe ₂ Pyr (0.47 mmol, 2 equiv.) in toluene (-40 °C, 3 mL) was added dropwise under stirring to a cold toluene solution (-40°C, 8 mL) of [W(NArcF ₃ )(CHCMe ₂ Ph)(OTf) ₂ (DME)] (203 mg, 0.23 mmol, 1 equiv.). The suspension was stirred overnight, affording an orange solution and an off-white precipitate. The solu- tion was filtered on Celite®, affording a clear orange solution, and taken to dryness to yield a dark orange oil. This oil was triturated with cold (-40°C) pentane (2 x 1.5 mL) to afford after drying in vacuo 108 mg of a light yellow powder (0.16 mmol, 69 %). ¹ H NMR (300 MHz, C ₆ H ₆ ) δ (ppm) 10.96 (s, 1 H, CHCMe ₂ Ph), 7.33 (m, 2H, Ph), 7.20-6.87 (m, 6H, Ph-Ar _CF3 ), 6.75 (m, 1 H, Ph), 6.52 (t, 1 H, Ar _CF 3, J = 8.0 Hz), 6.02 (br s, 6H, Me ₂ Pyr), 2.1 1 (br s, 12H, Me ₂ Pyr), 1 .58 (s, 6H, CHCMe ₂ Ph). ⁹ F NMR (200 MHz, C ₆ D ₆ ) δ (ppm) -60.4 (s, 3F, CF ₃ ).

2,2 Synthesis of supported catalysts

Example 1 : [(≡SiO)W(NAr)(CHC e ₃ )(OtBu)] (Ar = 2,6-iPr ₂ C ₆ H ₃ ) (representative procedure).

A solution of 104 mg of [W(NAr)(CHCMe ₃ )(OtBu) ₂ ] (0.181 mmol, 1.05 equiv.) in benzene (2 mL) was added to a suspension of Si0 _2- (7oo) (673 mg, 0.17 mmol) in benzene (2 mL) at room temperature. The suspension was slowly stirred at room temperature for 12h, resulting in a fading of the color of the solution and a coloration of the silica to yellow. The yellow solid was collected by filtration, and was washed by four suspension/filtration cycles in benzene (4 x 2 mL). The resulting yellow solid was dried thoroughly under high vacuum (10 ^~5 mBar) at room temperature for 3h to afford 672 mg of the title compound. All the filtrate solutions were collected and analyzed by ¹ H NMR spectroscopy in C ₆ D ₆ using ferrocene as internal standard (33,7 mg, 1 ,05 equiv.), indi- eating that 0.07 mmol of tBuOH were released upon grafting (0.4 tBuOH/W _SU rf). Elemental Analysis: W 3.32%, C 4,78%, H 0.68%, N 0.48% corresponding to 22 C/W (21 expected), 37.4 Η Λ (36 expected), 1 .9 N (1 expected). Example 2: [(≡SiO)W(NAr)(CHCMe ₃ )(OtBu _F3 )] (Ar = 2,6-iPr ₂ C ₆ H ₃ , tBu _F3 OH = (CF ₃ )Me ₂ COH)

From a solution of [W(NAr)(CHCMe ₃ )(OtBu _F 3)2(DME)] and a suspension of Si0 _2- (7oo) (500 mg, 0.13 mmol) in benzene (2 ml_) 552 mg of a yellow solid were isolated. All the filtrate solutions were collected and analysed by ¹ H NMR spectroscopy in C ₆ D ₆ using ferrocene as internal standard (11 mg, 1 equiv.), indicating that 0.1 1 mmol of tBu _F 30H were released upon grafting (0.85 tBu _F3 OH/W _surf ). Elemental Analysis: W 3.71 %, C 5.18%, H 0.72%, N 0.38% F 1.09% corresponding to 21 .4 C W (21 expected), 35.4 H/W (33 expected), 1 ,3 N (1 expected).

Example 3: [(=SiO)W(NAr)(CHC e ₃ )(OtBu _F6 )] (Ar = 2,6-iPr ₂ C ₆ H ₃ , tBu _F6 OH = (CF ₃ ) ₂ eCOH)

From a solution of 100 mg of [W(NAr)(CHCMe ₃ )(OtBu _F6 ) ₂ ] (0.13 mmol, 1 ,05 equiv.) in benzene (3 mL) and a suspension of Si0 _2- (7oo) (500 mg, 0.12 mmol) in benzene (2 mL), 512 mg of a light orange solid were isolated. All the filtrate solutions were collected and analysed by ¹ H NMR spectroscopy in C ₆ D ₆ using ferrocene as internal standard (1 1 .8 mg, 0.5 equiv.), indicating that 0.10 mmol of tBupeOH were released upon grafting (0.8 tBu _F6 OH/W _S urf). Elemental Analysis: W 3.88%, C 5.39%, H 0.65%, N 0.37%, F 2.05% corresponding to 21.3 C/W (21 expected), 30.6 H/W (30 expected), 1 ,3 N (1 expected).

Example 4: [(=SiO)W(NAr)(CHCMe ₃ )(OtBu _F9 )] (Ar = 2,6-iPr ₂ C ₆ H ₃ , tBu _F9 OH = (CF ₃ ) ₃ COH)

From a solution of 185.9 mg of [W(NAr)(CHCMe ₃ )(OtBu _F9 ) ₂ ] (0.21 mmol, 1 .05 equiv.) in benzene (4 mL) and a suspension of Si0 _2- (7oo) (790 mg, 0.12 mmol) in benzene (3 mL) 857 mg of an orange solid were isolated. Elemental Analysis: W 3.47%, C 4.84%, H 0.51 %, N 0.38%, F 3.14% corresponding to 21.3 C/W (21 expected), 26.8 H/W (27 expected), 1.4 N (1 expected). Example 5: [(≡SiO)W(NAr _C i)(CHC e ₂ Ph)(Me ₂ Pyr)] (Ar = 2,6-CI-C ₆ H ₃ , Me ₂ Pyr = 2,5-dimethylpyrrolide)

From a solution of 138 mg of [W(NAr _C i)(CHCMe ₂ Ph)(Me ₂ Pyr) ₂ ] (0.21 mmol, 1.05 equiv.) in benzene (3 mL) and a suspension of Si0 _2-(7 oo) (800 mg, 0.20 mmol) in benzene (2 mL) 790 mg of a light brown solid were isolated. All the filtrate solutions were collected and analyzed by ¹ H NMR spectroscopy in C ₆ D ₆ using ferrocene as internal standard (38.7 mg, 1 equiv.), indicating that 0.13 mmol of Me ₂ PyrH were released upon grafting (0.7 Me ₂ PyrH/W _surf ).

Example 6: [(≡SiO)W(NArci)(CHCMe ₂ Ph)(OtBu _F6 )], (Ar _a = 2,6-CI-C ₆ H ₃ , tBu _F6 OH = (CF ₃ ) ₂ MeCOH))

From a solution of 101 mg of [W(NArci)(CHCMe ₃ )(OtBu _F6 )2] (0.13 mmol, 1 ,05 equiv.) in benzene (2 mL) and a suspension of Si0 _2-(7 oo) (463 mg, 0.12 mmol) in benzene (2 mL), 450 mg of a light orange solid were isolated. All the filtrate solutions were collected and analysed by ¹ H NMR spectroscopy in C ₆ D ₆ using ferrocene as internal standard (22.3 mg, 1 equiv.), indicating that 0.08 mmol of tBu _F6 OH were released upon grafting (0.7 tBu _F6 OH/W _surf ). Example 7: [(≡SiO)W(NAr _cl )(CHCMe ₂ Ph)(OtBu _F9 )], (Ar _C i = 2,6-CI-C ₆ H ₃ , tBu _F9 OH = (CF ₃ ) ₃ COH))

From a solution of 98.5 mg of [W(NAr _C i)(CHCMe ₂ Ph)(OtBu _F 9)2(DME)] (0.10 mmol, 1 ,05 equiv.) in benzene (2 mL) and a suspension of Si0 _2- ( ₇ oo) (365 mg, 0.09 mmol) in ben ^¬ zene (2 mL) 360 mg of a light orange solid were obtained. All the filtrate solutions were collected and analysed by ¹ H NMR spectroscopy in C ₆ D ₆ using ferrocene as internal standard (17.7 mg, 1 equiv.), indicating that 0.09 mmol of DME were released upon grafting (0.9 DME/W _surf ).

Example 8: [(=SiO)W(NAr _CF3 )(CHCMe ₂ Ph)(Me ₂ Pyr)] (Ar _CF3 = 2-CF ₃ -C ₆ H ₄ , Me ₂ Pyr = 2,5-dimethylpyrrolide)

From a solution of 75 mg of [W(NAr _CF3 )(CHCMe ₂ Ph)(Me ₂ Pyr) ₂ ] (0.1 1 mmol, 1 ,05 equiv.) in benzene (3 mL) and a suspension of Si0 _2-(70 o) (403 mg, 0.10 mmol) in ben ^¬ zene (2 mL), 390 mg of a yellow solid were isolated. All the filtrate solutions were collected and analysed by ¹ H NMR spectroscopy in C ₆ D ₆ using ferrocene as internal standard (38.7 mg, 1 equiv.), indicating that 0.09 mmol of Me ₂ PyrH were released upon grafting (0.95 Me ₂ PyrH/W _SU rf). Example 9: [(=SiO)W(NAr _C i)(CHCMe ₂ Ph)(OtBu)] Ar _Cf = 2,6-CI-C ₆ H ₃

A solution of 100 mg of [W(NArci)(CHCMe ₂ Ph)(OtBu) ₂ ] (0.16 mmol, 1.05 equiv.) in cold toluene (2 mL, -40 °C) was added to a suspension of Si0 _2- ( ₇ oo) (576 mg, 0.15 mmol) in cold toluene (2 mL, -40 °C). The suspension was slowly stirred at room tempera- ture for 30 min, resulting in a fading of the color of the solution and a coloration of the silica to orange. The orange solid was collected by filtration, and was washed by four suspension/filtration cycles in benzene (4 x 2 mL). The resulting orange solid was dried thoroughly under high vacuum (10 ^~5 mBar) at room temperature for 5h to afford 1 10 mg of the title compound. All the filtrate solutions were collected and analysed by ¹ H NMR spectroscopy in C ₆ D ₆ using ferrocene as internal standard (27.9 mg, 1 equiv.), indicating that 0.12 mmol of tBuOH were released upon grafting (0.8 tBuOH/W _surf ).

Example 10: [(≡SiO)Mo(NAr _cl )(CHCMe ₂ Ph)( e2Pyr)] (Ar _C i = 2,6-CI-C ₆ H ₃₎ Me ₂ Pyr = 2,5-dimethylpyrrolide)

From a solution of 113 mg of [Mo(NAr _C i)(CHCMe ₂ Ph)(Me ₂ Pyr) ₂ ] (0.20 mmol, 1 .05 equiv.) in benzene (3 mL) and a suspension of Si0 _2-(70 o) (710 mg, 0.19 mmol) in benzene (2 mL), 690 mg of a red solid were isolated. All the filtrate solutions were collected and analyzed by ¹ H NMR spectroscopy in CeD ₆ using ferrocene as internal stand- ard (34.5 mg, 1 equiv.), indicating that 0.14 mmol of Me ₂ PyrH were released upon grafting (0.75 Me ₂ PyrH/W _surf ).

Example 11 : [(=SiO)Mo(NAr)(CHCMe ₃ )(OC(CF ₃ ) ₂ Ph)] (Ar = 2,6-iPr ₂ C ₆ H ₃ )

From a solution of 125 mg of [W(NAr)(CHCMe ₃ )(OC(CF ₃ ) ₂ Ph) ₂ ] (0.14 mmol, 1 .05 equiv.) in benzene (3 mL) and a suspension of Si0 _2-(70 o) (510 mg, 0.13 mmol) in benzene (2 mL), 517 mg of a yellow green solid were isolated. All the filtrate solutions were collected and analyzed by ¹ H NMR spectroscopy in C ₆ D ₆ using ferrocene as internal standard (26.0 mg, 1 equiv.), indicating that 0.12 mmol of HOC(CF ₃ ) ₂ Ph were released upon grafting (0.9 HOC(CF ₃ ) ₂ Ph /W _s „rf).

Example 12: [(=SiO)Mo(NAr)(CHCMe ₂ Ph)(OtBu _F6 )] (Ar = 2,6-iPr ₂ C ₆ H ₃ )

(N. Rendon et. al., Chem. Eur. J. 2009, 15, 5083-5089) Example 13: [(≡SiO)W(NAr)(CHCMe ₂ Ph)(OSiPh ₃ )] (Ar = 2,6-iPr ₂ C ₆ H ₃ )

From a solution of 241 mg of [W(NAr)(CHCMe ₂ Ph)(OSiPh) ₂ ] (0,21 mmol, 1 ,05 equiv.) in benzene (4 ml_) and a suspension of Si0 _2- (7oo) (810 mg, 0,23 mmol) in benzene (2 mL), a light orange solid were isolated. All the filtrate solutions were collected and analyzed by ¹ H NMR spectroscopy in C ₆ D ₆ using ferrocene as internal standard (52.3 mg, 1.33 equiv.), indicating that 0.48 mmol of HOSiPh ₃ were released upon grafting.

Example 14: [(≡SiO)W(NAr)(CHCMe ₃ )(Me ₂ Pyr)] (Ar = 2,6-iPr ₂ C ₆ H ₃ )

(F. Blanc et al., Proc. Nat. Acad. Sci. 2008, 12123)

Example 15: [(≡SiO)Mo(NAr)(CHCMe ₂ Ph)(Me ₂ Pyr)] (Ar = 2,6-iPr ₂ C ₆ H ₃ )

(F. Blanc et al., J. Amer. Chem. Soc. 2007, 129, 8434-8435) Example 16: [(=SiO)W(NAr _F5 )(CHCMe ₂ Ph)(Me ₂ Pyr)] (Ar _FS = C ₆ F ₅ )

From a solution of 59 mg of [W(NC ₆ F ₅ )(CHCMe ₂ Ph)(Me ₂ Pyr)2] (0.086 mmol, 1 .05 equiv.) in benzene (3 mL) and a suspension of Si0 _2-(70 o) (314 mg, 0.082 mmol) in benzene (3 mL), 343 mg of a orange-yellow solid were isolated. All the filtrate solutions were collected and analyzed by ¹ H NMR spectroscopy in C ₆ D ₆ using ferrocene as an internal standard, indicating that 0.07 mmol of Me ₂ PyrH were released upon grafting (0.9 Me ₂ PyrH W _surf ). Elemental Analysis: W 4.13%, C 5.95%, H 0.48%, N 0.77% F 2.17% corresponding to 22.1 C W (22 expected), 21 .2 H/W (20 expected), 2.4 N (2 expected), 5.1 F (5 expected). Example 17: [(≡SiO)W(NAr)(CHCMe ₂ Ph)(OAr _F5 )] (Ar = 2,6-iPr ₂ C ₆ H ₃ ) (Ar _F5 = C ₆ F ₅ )

3. Catalytic activity

3.1 Ethenolysis of 9-octadecene:

9-Octadecene (E/Z isomer mixture) was purified by fractional distillation under inert atmosphere at reduced pressure (1 mbar) then it was percolated through a column of activated aluminum oxide 90 (basic, Brockman I, dried at 300 °C under 0.1 mbar vacuum for 24 h; column: d = 4 cm, I = 15 cm for 1 L of 9-octadecene) and was kept under inert atmosphere.

In a nitrogen gas filled glove-box the calculated amount (0.5 - 5 ml_) of 9-octadecene was added to the silica supported catalyst (3-5 mg) measured into a 30 ml glass vial. The vial was placed into a stainless steel autoclave and the reaction mixture was stirred by a magnetic stir bar under 10 atm of ethylene overpressure at room temperature for the specified time (see results table). The excess of ethylene was let out from the autoclave, the reaction mixture was quenched by wet ethyl acetate and the reaction mixture was analyzed by GC-FID (Shimadzu GC-2010 Plus; Zebron ZB-35HT Inferno).

The subsequent table summarizes the results obtained with selected catalysts:

3.2 Ethenolysis of a triglyceride (rape-seed oil)

Commercially available edible grade rapeseed oil sample (1 mL) was treated by 6.5 mol% triethylaluminium. Then 0.1 mol-% of the grafted silica catalyst was added. The reaction mixture was stirred in a stainless steel autoclave under 10 bar of ethylene atmosphere at 50 °C for 16 hours. To the reaction mixture sodium methylate in methanol (0.5 M, 20 mL) was added and the mixture was stirred at room temperature for 3 hours. After the end of the transesterification an aliquot (2 mL) was let through a small (7 mL) column of silica gel and the column was washed by tetrahydrofurane (25 mL). The combined elute was analyzed by GCMS-FID using heptadecane as internal standard. The resulting yield relates to methyl decenoate which has been formed in the transesterifica- tion reaction.

Catalyst Conversion Yield of

(%) methyl decenoate (%)

Example 8: [(≡SiO)W(NAr _C F3)(CHCMe ₂ Ph)(Me ₂ Pyr)] 34 16

Example 16: [(≡SiO)W(NAr _F5 )(CHCMe ₂ Ph)(Me ₂ Pyr)] 66 38