Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 101. Synthesis of the compounds [WPt(µ-CC6H4Me-4)(µ-σ:ηx-C2BnHn–1Me2)(CO)2(PMe2Ph)2](x= 5, n= 9; x= 6, n= 10); crystal structures of an isomer of each complex
- 1 January 1990
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 8,p. 2617-2624
- https://doi.org/10.1039/dt9900002617
Abstract
In acetone at ambient temperatures, the reagents [PtCl(Me)(PMe2Ph)2], TIBF4, and [NEt4][W(CC6H4Me-4)(CO)2(η5-C2B9H9Me2)] afforded [WPt(µ-CC6H4Me-4)(µ-σ:η5-C2B9H8Me2)(CO)2(PMe2Ph)2](two isomers), and a small amount of a salt formulated as [PtMe(PMe2Ph)3][W2Pt(µ-CC6H4Me-4)2(µ-σ:η5-C2B9H8Me2)(CO)4(η5-C2B9H9Me2)]. The structure of one isomer of the dimetal compound was determined by X-ray diffraction. The W–Pt bond [2.720(1)Å] is spanned by the p-tolylmethylidyne group [W–µ-C 1.89(1), Pt–µ-C 2.14(1)Å] and by a C2B9 fragment. The latter is co-ordinated to the W atom via the open pentagonal face of the nido-icosahedral cage, and bridges to the Pt atom through an exopolyhedral B–Pt σ bond [2.17(1)Å]. This boron atom is in the β site with respect to the carbon atoms in the [graphic omitted] ring. In the other isomer it is the boron α to a carbon atom which forms the B–Pt bond. The reaction between the compounds [PtCl(Me)(PMe2Ph)2],TIBF4, and [NEt4][W(CC6H4Me-4)(CO)2(η6-C2B10H10Me2)] in thf (tetrahydrofuran) also yields two isomers of a dimetal species [WPt(µ-CC6H4Me-4)(µ-σ:η6-C2B10H9Me2)(CO)2(PMe2Ph)2]. The structure of the isomer formed in greatest yield (ca. 70%) was established by X-ray diffraction. The W–Pt bond [2.738(1)Å] is bridged by the alkylidyne group [W–µ-C 1.92(1), Pt–µ-C 2.14(1)Å] and by a C2B10 fragment. The non-planar [graphic omitted] face of the latter is η6 co-ordinated to the tungsten, but the cage also forms a B–Pt σ bond [2.15(1)Å]. This linkage involves a boron atom of the B3 group α to a carbon, and correspondingly the other isomer is assigned a structure in which it is the [graphic omitted] atom of the hexagonal ring which bonds to platinum. The n.m.r. data (1H, 13C-{1H}, 11B-{1H}, and 31P-{1H}) for the new compounds are reported, and are in agreement with the structures proposed.Keywords
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