Article
Reaction of Silafluorenes with (Ph3P)2Pt(η2-C2H4): Generation and Characterization of Pt−Si Monomers, Dimers, and Trimers
Organometallics
(2004)
Abstract
The reaction of silafluorene (1; H2SiC12H8) with (Ph3P)2Pt(η2-C2H4) (2) at room temperature in C7D8 initially provided the mononuclear complex (Ph3P)2Pt(H)[Si(H)C12H8] (3), followed by the appearance of the unsymmetrical dinuclear complex (Ph3P)2(H)Pt(μ-SiC12H8)(μ-η2-HSiC12H8)Pt(PPh3) (4) and finally the novel trinuclear complex [(Ph3P)Pt(μ-SiC12H8)]3 (5). The three complexes were characterized by multinuclear NMR spectroscopy and by X-ray crystallography (5). The molecular structure of 5 exhibits a nonplanar Pt3Si3 core. When the reaction was conducted at low temperature until the silafluorene was consumed and the mixture then warmed to room temperature, the dinuclear complex 4 could be isolated. The related substituted silafluorene system 3,7-di-tert-butylsilafluorene (6; H2SiC20H24) also reacted with 2 to provide both mono- and dinuclear complexes (7 and 8) analogous to 3 and 4. The dinuclear complex 8 was isolated and crystallographically characterized. Each of the two Pt centers in complex 8 exhibits a unique environment. In solution at low temperature 8 is best described as having one platinum center with a terminal hydride, [Pt(H)(PPh3)2], and the second platinum with a nonclassical [Si···H···Pt(PPh3)] unit. However, in the solid state, the two hydrides may both adopt a bridging environment. Heating a sample of the unsymmetrical dimer 8 led to the formation of several products, one of which was the trimer 9, analogous to 5.
Disciplines
Publication Date
2004
DOI
10.1021/om0400447
Citation Information
Janet Wilking, Joyce Y. Corey, Kevin A. Trankler, Kimberly Dill, et al.. "Reaction of Silafluorenes with (Ph3P)2Pt(η2-C2H4): Generation and Characterization of Pt−Si Monomers, Dimers, and Trimers" Organometallics Vol. 23 Iss. 23 (2004) p. 4576 - 4584 Available at: http://works.bepress.com/janet-braddock-wilking/43/