- Hexamethyl tungsten
Name = Hexamethyl tungsten
ImageFile = Hexamethyltungsten-2D-dimensions.png
ImageName = Hexamethyl tungsten
ImageFileL1 = Hexamethyl-tungsten-3D-balls.png
ImageNameL1 = Ball-and-stick model of hexamethyl tungsten
ImageFileR1 = Hexamethyl-tungsten-3D-polyhedra.png
ImageName2 = Polyhedral model of hexamethyl tungsten
IUPACName = Hexamethyl tungsten
OtherNames = Tungsten hexamethyl
Section1 = Chembox Identifiers
CASNo = 36133-73-0
Section2 = Chembox Properties
Formula = (CH3)6W
MolarMass = 274.06 g/mol
Appearance = red crystalline solid
MeltingPt = 30 °C (303 K)
Section3 = Chembox Structure
MolShape = trigonal prismatic
Hexamethyl tungsten is the
chemical compoundW(CH3)6. Classified as an organometalliccompound, hexamethyl tungsten is an air-sensitive, red, crystalline solid at room temperature; however, it is extremely volatile and sublimes at −30 °C. Owing to its six methyl groups it is extremely soluble in petroleum, aromatic hydrocarbons, ethers, carbon disulfide, and carbon tetrachloride.Shortland, A. J.; Wilkinson, G."J. Chem. Soc., Dalton Trans."1973, 872-876.] The compound is unknown in nature. [Koutsospyros, A.; Braida, W.; Christodoulatos, C.; Dermatas D.; N. Strigul, N.;"Journal of Hazardous Materials"2006,"136", 1-19] .
Hexamethyl tungsten was first reported synthesized in 1973 by Wilkinson and Shortland by reacting
methyl lithiumwith tungsten hexachloridein diethyl ether. Unfortunately, this method is quoted as frequently giving poor or sometimes zero yields.Fact|date=October 2007 Geoffrey Wilkinsonwas awarded a share of the [http://nobelprize.org/nobel_prizes/chemistry/laureates/1973/ 1973 Nobel Prize in Chemistry] for his work on organometallic compounds.
In 1976, Wilkinson and Galyer reported on an improved synthesis of W(CH3)6 using
trimethylaluminiuminstead of methyl lithium, and the use of trimethylamine. [Galyer, A. L.; Wilkinson, G."J. Chem. Soc., Dalton Trans."1976, 2235-8] The stoichiometry of the improved synthesis is as follows:
:WCl6 + 6Al(CH3)3 → W(CH3)6 + 6Al(CH3)2Cl
W(CH3)6 has a distorted
trigonal prismatic geometrywith C3v symmetry. The trigonal prismatic geometry is unusual, in that the vast majority of six-coordinate organometallics have octahedral molecular geometry. W(CH3)6 has an interesting history in terms of identifying its molecular structure. When it was initially synthesized, Wilkinson et al believed that W(CH3)6 would have an octahedral structure. In fact, the initial motive for synthesizing the compound was based on previous work with tetrahedralmethyl transition metalcompounds, which are thermally unstable, in the hopes that an octahedral methyl compound would prove to be more stable. In the initial report, the IR spectroscopyresults were consistent with an octahedral structure. In 1978, a study using photoelectron spectroscopy confirmed the initial Oh assignment. [Green, J. C.; Lloyd, D. R.; Galyer, L.; Mertis, K.; Wilkinson, G."J. Chem. Soc., Dalton Trans."1978, 1403-7]
The octahedral assignment remained for nearly 20 years after its discovery. In 1989, Girolami and Morse reported that [Zr(CH3)6] 2- did not have octahedral geometry as previously believed, but rather trigonal prismatic geometry based on their
X-ray crystallographyresults. [Morse, P. M.; Girolami, G. S."J. Am. Chem. Soc."1989,"111", 4114-6] They predicted that other d0 ML6 species such as [NbMe6] -, [TaMe6] -, and W(CH3)6 would also prove to be trigonal prismatic. This prompted others to investigate the structure of W(CH3)6 in more detail, and in 1990 Volden et al made the first confirmation that W(CH3)6 did indeed have trigonal prismatic structure with D3h or C3v symmetry based on their results from gas-phase electron diffraction. [Haalan, A.; Hammel, A.; Rydpal, K.; Volden, H. V."J. Am. Chem. Soc."1990,"112", 4547-4549.] In 1996, Seppelt et al. reported that W(CH3)6 had a strongly distorted trigonal prismatic coordination geometryfrom their work with single-crystal X-ray diffraction, which they later confirmed in 1998. [Seppelt, K.; Pfennig, V."Science"1996,"271", 626-8.] [Kleinhenz, S.; Pfennig, V.; Seppelt, K.;"Chem. Eur. J."1998,"4", 1687-91.]
As shown in the top figure at right, the ideal or D3h trigonal prism in which all six carbons are equivalent is distorted to the C3v structure observed by Seppelt et al. by opening up one triplet of methyl groups (upper triangle) to wider C-W-C angles (94-97°) with slightly shorter C-W bond lengths, while closing the other triplet (lower triangle) to 75-78° with longer bond lengths.
Deviation from octahedral geometry can be ascribed to the
electronic configurationof the central atom, tungstenin this case, and an effect known as Jahn-Teller distortion.Seppelt, K."Accounts of Chemical Research"2003,"36(2)", 147-153] [Kaupp, M."Chemistry - A European Journal"1998,"4(9)", 1678-86] . In 1995, before the work of Seppelt and Pfennig, Landis and coworkers had already predicted a distorted trigonal prismatic structure based on valence bond theoryand VALBONDcalculations. [Landis, C. K.; Cleveland, T.; Firman, T. K. Making sense of the shapes of simple metal hydrides. "J. Am. Chem. Soc." 1995, "117", 1859-1860.] [Landis, C. K.; Cleveland, T.; Firman, T. K. Structure of W(CH3)6. "Science" 1996, "272", 182-183.] The interested reader is encouraged to read "Nonoctahedral Structures" by Konrad Seppelt for a more rigorous treatment. The history of elucidating the structure of W(CH3)6 illustrates an inherent difficulty in interpreting spectral data for new compounds: initial data may not provide reason to believe the structure deviates from a presumed geometry based on significant historical precedence, but there is always the possibility that the initial assignment will prove to be incorrect. Prior to 1989, there was no reason to suspect that ML6 compounds were anything but octahedral, yet new evidence and improved characterization methods suggested that perhaps there were exceptions to the rule, as evidenced by the case of W(CH3)6. These discoveries helped to spawn re-evaluation of the theoretical considerations for ML6 geometries.
Other 6-coordinate complexes with distorted trigonal prismatic structures include [MoMe6] , [NbMe6] -, and [TaPh6] -. All are d0 complexes. Some 6-coordinate complexes with regular trigonal prismatic structures (D3h symmetry) include [ReMe6] (d1), [TaMe6] - (d0), and the aforementioned [ZrMe6] 2- (d0). [Housecroft, C. E.; Sharpe, A. G.(2005)"Inorganic Chemistry" 2nd ed. Pearson Education Limited: England.]
room temperature, hexamethyl tungsten will decompose to give off methaneand trace amounts of ethane. The black residue that remains is purported to contain polymethyleneand tungsten, but the decomposition of W(CH3)6 to form tungsten metal is highly unlikely. The following equation is the approximate stoichiometryproposed by Wilkinson and Shortland:
Oxygen: W(CH3)6 is spontaneously flammable in air.
- Acidic protons: W(CH3)6 reacts with compounds containing acidic protons to release
methane. Halogens: W(CH3)6 reacts with halogenssuch as bromineand iodineto release the methyl halideand leave the tungsten halide.
A patent application was submitted in 1991 suggesting the use of W(CH3)6 in the manufacture of
semiconductordevices during the chemical vapor depositionof tungsten thin films; [Matsumoto, S.; Ikeda, O.; Ohmi, K. (Canon K. K., Japan)."Eur. Pat. Appl."1991] however, to date it has not been used for this purpose. WF6(g) + H2(g) is used instead. [Kirss, R. U.; Meda, L."Applied Organometallic Chemistry"1998,"12(3)", 155–160]
afety and pollution considerations
W(CH3)6 should be handled with extreme care due to the risk of explosions, even in the absence of air. Serious explosions have been reported as a result of working with the compound. [Mertis, K.; Galyer, L.; Wilkinson, G."Journal of Organometallic Chemistry"1975,"97(3)", C65.] [Green, J.C.; Lloyd, D. R.; Galyer, L.; Mertis, K.; Wilkinson, G."Inorganic Chemistry"1978,"(10)", 1403-7.]
*Sir Geoffrey Wilkinson
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