APPLICATIONS OF METAL COMPLEX COMPOUNDS

Field of the Invention

The present invention relates to metal complex compounds and their reactions with small gaseous molecules. More specifically it is concerned with the use of uranium complexes in the treatment of gases such as the oxides of carbon, nitrogen and sulphur.

Background to the Invention

The problems associated with the generation of so-called "greenhouse gases", and their role in the phenomenon of global warming, are well known and much attention has been devoted to the development of different means by which the volumes of such gases released in emissions may be reduced. Thus, for example, the production of large volumes of greenhouse gases by electricity generation associated with the burning of fossil fuels has resulted in greater interest in alternative means of generation, such as wind, wave and solar power, as well as nuclear power generation. Also, greenhouse gas emission associated with various modes of transport - and most particularly with the rapid growth in use of the internal combustion engine and in the use of air transport - has resulted in significant efforts being made in various quarters to reduce the frequency and distance of journeys.

There seems, however, to be little doubt that, whatever efforts may be made to reduce the volumes of greenhouse gases which are emitted into the atmosphere, their presence will continue to cause problems for many years to come, since it would be impossible to change with sufficient rapidity systems and devices which are already well established commercially. Consequently, attention has also turned to alternative approaches, wherein the greenhouse gases which are emitted are subsequently treated so as to reduce or eliminate the volumes which are released into the atmosphere.

One obvious approach to this problem in certain situations is the use of scrubbers, which are designed to remove the greenhouse gases from the gaseous effluent by reaction or dissolution in a liquid - typically aqueous - scrubbing medium. The disadvantage with this approach, however, is that whilst volumes of gaseous effluents may be significantly reduced in this way, different problems are created as the result of the generation of significant volumes of liquid effluents.

An alternative means of addressing the problem may involve the use of adsorbents, such as activated charcoal, over which the gases are allowed to pass, the specific adsorbent being chosen so as to preferentially adsorb the greenhouse gases which are of particular concern from an environmental perspective in a given situation. However, the large volumes of gases which often have to be treated would typically require the use of significant amounts of adsorbent, with the attendant problems of cost and disposal of adsorbent.

A more successful approach may be by the use of materials which are capable of chemical reaction with - rather than simple physical adsorption of - these greenhouse gases, and this is the approach adopted by the present inventors. Many previous efforts in this field have, however, utilised very aggressive, hazardous and expensive techniques. Thus, for example, the removal of carbon monoxide has typically been achieved via methods such as reductive cyclomerisation using media such as alkali metals in iiquid ammonia, or by means of electrolysis procedures. The present inventors have sought to adopt a more convenient and less hazardous approach to the solution of the problem.

There are described in WO-A-99/09034 complexes of trivalent metals, principally thorium and uranium, which find particular use as nitrogen fixation agents, for the production of precursors for ammonia production, and for inserting nitrogen into compounds during synthesis reactions. The disclosed complexes incorporate dinitrogen in their structure and illustrate the capture of a small molecule in a larger metal complex molecule. However, the disclosed complexes are exclusively based on the formation of structures incorporating an inert, symmetrical structure, in the form of nitrogen.

Compounds incorporating uranium which could be used in the preparation of the complexes disclosed in WO-A-9909034 were previously known from WO-98/20971 , wherein there were disclosed compounds, and particularly catalysts, which comprised complexes of actinides with at least one ϋgand, the disclosed compounds being described as finding particular use in the catalysis of polymerisation reactions. This document contained no suggestion of the use of the said compounds in the preparation of complexes by the incorporation of small molecules.

The present inventors have sought to develop an approach by means of which complexes may be formed by the chemical interaction of compounds with small

molecules, specifically the small gaseous molecules which comprise greenhouse gases, and thereby allow these gases to be removed from the atmosphere. Surprisingiy, it has been found that polar molecules of the greenhouse gases are capable of complex formation with certain complexes of actinide metals, specifically complexes wherein the actinide meta! is in the trivalent state.

Summary of the Invention

Thus, according to a first aspect of the present invention, there is provided a method for binding gaseous molecules, said method comprising contacting gases comprising said gaseous molecules with trivalent meta! complexes.

Said gaseous molecules typically may comprise polar gaseous molecules, most particularly molecules of greenhouse gases, especially the oxides of carbon, nitrogen and sulphur. Most particularly, said gases comprise carbon monoxide, carbon dioxide, nitrogen monoxide, nitrogen dioxide, dinitrogen monoxide and sulphur dioxide, but the use of the method of the invention with polar gaseous molecules such as ammonia, hydrogen sulphide and carbon disulphide is also envisaged, as well as with hydrogen and hydrocarbons such as methane. The procedure of the invention results in the reductive combination of the target gaseous molecules such that, in the case of the oxides of carbon, for example, higher oxygenated hydrocarbons are produced.

The method of the invention may be carried out at ambient temperature and pressure and, as such, offers significant advantages over the methods of the prior art.

Preferably, the trivalent metal complexes which are useful in the context of the method of the present invention comprise complexes of actinide metals, most preferably uranium. Alternatively, said metal complexes may comprise complexes of transition metals, such as titanium, zirconium or hafnium. Particularly preferably, said complexes comprise sandwich complexes. Most preferably, said complexes comprise sandwich complexes of uranium which comprise two aromatic ring systems. Typicaiiy, said aromatic ring systems comprise C ₅ to C ₁₀ aromatic rings including, for example, pentalenyl, indenyl, cyclopentadienyl and cyciooctatetraenyl rings. Especially preferred are the C ₅ to C ₈ aromatic ring systems.

According to a second aspect of the present invention, there is provided a trivalent metal complex comprising a sandwich complex of a metal, wherein said metal comprises a

trivalent metal which is selected from transition metals and actinide metals, said complex comprising two ligands selected from indenyl, cyciopentadienyl and cyclooctatetraenyl tigands.

Optionally, said iigands may be unsubstituted or, alternatively, they may be substituted with from 1 to 5 ring substituents. Typically said ring substituent groups comprise groups selected from aikyl, siiyl and alkylsiiyl groups, with C _1-5 alkyl and alkylsily! groups being most preferred. Particularly preferred in this respect are methyl groups, butyl groups, preferably tertiary butyi groups, methylsϋyl groups and propyisilyl groups, most particularly isopropyisϋyi groups. The preferred substituents may comprise mono-, di-, or trialkylsilyl groups, and the most preferred groups are trimethylsilyl and triisopropylsilyl groups.

Preferred examples of the complexes of the second aspect of the invention include 1 ,4- di(trialkylsιlyl)cyclooctatetraene/methylated cyciopentadienyl mixed sandwich uranium(lil) complexes (I), 1,4-di(trialky!silyl)pentalene/methylated cyciopentadienyl mixed sandwich uranium(ill) complexes (II), and 1,4- di(trialkylsilyl)cyclooctatetraene/methyl(silyl)ated indenyl mixed sandwich uranium(lll) complexes (III).

ii U l

In (I) and (II): R - -CH ₃ or -CH(CH ₃ V, R' = -CH ₃ , -C(CH ₃ ) ₃ or Si(CH ₃ ) ₃ ; when R ¹ = -CH ₃ , n = 1-5, and when R' = -C(CH ₃ ) ₃ or Si(CH ₃ ) ₃ , n = 1-3,

In (III): R = -CH ₃ or ~~CH(CH ₃ ) ₂ ; R' = -CH ₃ , -CH(CH ₃ ) ₂ , -C(CH ₃ ) ₃ or Si(CH ₃ ) ₃ ; when R' = -CH ₃ , P = 1-3, and when R' = -CH(CH ₃ ) ₂ , -C(CH ₃ ) ₃ or Si(CH ₃ ) ₃ , p - 1-2; R" = CH ₃ ; r = 0-4.

A particularly preferred complex in the context of the first and second aspects of the invention comprises a 1 ^-diftriisopropylsilyOcyclooctatetraene/methyiated cyclopentadienyl mixed sandwich uranium(iil) complex, most preferably a 1,4- dKtriisopropyisilyOcyclooctatetraene/pentamethy!-, tetramethyl- or trimethyl- cyclopentadienyl mixed sandwich uranium(lll) complex. Said complex may be caused to react with carbon monoxide so as to form a deltate or squarate derivative comprising two molecules of the complex linked by the deltate or squarate ring.

The complexes according to the second aspect of the invention are typically prepared from the metals via the corresponding metal halides. Thus, according to a third aspect of the invention, there is provided a method for the preparation of a trivalent metal complex, said method comprising:

(a) reacting the metal with a halide salt; (b) reacting the resulting metal halide with a first metal aromatic compound; and

(c) reacting the intermediate so formed with a second metal aromatic compound.

Particularly suitable halide salts for use in the first stage of the synthesis are mercury(li) halides, most particularly rπercury{ll) iodide. The reactions are typically carried out at elevated temperatures over a prolonged period of time in a sealed tube.

The metal aromatic compounds used in the formation of the complex are preferably alkali metal aromatic compounds, most particularly potassium aromatic compounds such as pentamethyl-, tetramethyl- or trimethyl-cyclopentadienyl potassium and 1 ,4- di(triisopropylsilyl) cyclooctatetraenyl dipotassium. Reaction of these compounds with the metal halide are typically carried out in organic solvents such as tetrahydrofuran at room temperature and pressure.

Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of the words, for example "comprising" and "comprises", means "including but not limited to", and is not intended to (and does not) exclude other moieties, additives, components, integers or steps.

Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

Features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith.

Detailed Description of the Invention

A particularly preferred embodiment of the compounds according to the second aspect of the invention comprises a i^-diftriisopropylsilyOcyclooctatetraene/pentamethyl-, tetramethyl- or trimethyl-cyclopentadienyl mixed sandwich uranium(!l!) complex. These complexes may be prepared from uranium turnings by firstly reacting the uranium with mercury(il) iodide at 32O ⁰ C for 2 days in a sealed tube. The resulting uranium(III) iodide is then reacted firstly with pentamethyl-, tetramethyl- or trimethyl-cyclopentadieny! potassium and then with 1 ,4-di(triisopropylsilyl)cyc!ooctatetraenyl dipotassium, both reactions being carried out at room temperature and pressure in tetrahydrofuran.

Further preferred embodiments of the second aspect of the invention include 1 ,4- di(triisopropylsilyl)cyc!ooctatetraene/cyclopentadieny! mixed sandwich uranium{IH) complexes wherein the cyclopentadiene ring is substituted with alkyl groups other than methyl groups. Preferred alkyl groups include butyl groups, most preferably t-butyl groups. In other preferred embodiments, the substituents comprise mono-, di-, or trialkyisilyl groups, and the most preferred groups in this context are trimethylsilyi groups. Some or all of the ring carbon atoms of the cyciopentadiene ring may be substituted with the aforementioned groups but, preferably, the ring carries 3, 4 or 5 substituents, and these substituents may be the same or different.

Specific examples of preferred compounds in the context of the present invention include the 1 ,4-di(triisopropy!silyi)cyc!ooctatetraene/pentamethylcyciope ntadienyl mixed sandwich uranium(lll) complex (IV), the i ^-dKtriisopropyisilylJcyclooctatetraene/ tetrametbylcyciopentadienyl mixed sandwich uraniurn(ill) complex (V), and the 1,4- dKtriisopropyisilyOcyciooctatetraene/hexamethylindenyi mixed sandwich uranium(lll) complex (V!).

IV V Vl

The complexes which are so obtained are found to react with carbon monoxide at atmospheric pressure at temperatures anywhere between -78° and 25°C in an inert solvent such as diethyl ether or toluene to form squarate or deltate derivatives. Similar results have been successfully achieved by the reaction of the complexes with carbon dioxide, whilst the complexes may also activate nitrogen monoxide, ammonia, sulphur dioxide and carbon disulphide.

The method according to the first aspect of the present invention provides an efficient and convenient means for the removal of gases such as the oxides of carbon, nitrogen and sulphur from the atmosphere through their reaction with the metal complexes, including those according to the second aspect of the invention. Accordingly, the method according to the first aspect of the invention is particularly useful in the removal of so-called greenhouse gases from the atmosphere, and is therefore of potentially very great value environmentally.