173603-05-9Relevant academic research and scientific papers
Reactions of the square-planar compounds Ir(C2Ph)L2(PCy3) (L2 = 2 CO, TFB) with HSiR3 (R = Et, Ph) and Hx+1SiPh3-x (x = 1, 2): Stoichiometric and catalytic formation of Si-C bonds
Esteruelas, Miguel A.,Oliván, Montserrat,Oro, Luis A.
, p. 814 - 822 (1996)
The square-planar cis-dicarbonyl complex Ir(C2Ph)(CO)2(PCy3) (1) reacts with ca. 1 equiv of HSiR3 to give, in quantitative yield, the corresponding alkynyl-hydrido-silyl derivatives Ir(C2Ph)(H)(SiR3)(CO)2(PCy3) (SiR3 = SiEt3 (2), SiPh3 (3), SiHPh2 (4), and SiH2Ph (5)). The reactivity of the related tetrafluorobenzobarrelene compound Ir(C2Ph)(TFB)(PCy3) (6) toward HSiR3 has been also studied by NMR spectroscopy. The addition of ca. 2 equiv of HSiEt3 to a benzene-d6 solution of 6 affords IrH2(SiEt3)(TFB)(PCy3) (7) and PhC=CSiEt3 in a 1:1 molar ratio, while the reaction of 6 with ca. 1 equiv of HSiPh3 yields, after 1 h and 30 min, IrH2-(SiPh3)(TFB)(PCy3) (10, 8%), Ir{C(SiPh3)=CHPh}(TFB)(PCy3) (11, 52%), and PhC=CSiPh3 (8%). The addition of ca. 1 equiv of H2SiPh2 to a benzene-d6 solution of 6 leads, after 1 h, to IrH2{Si(C2Ph)Ph2}(TFB)(PCy3) (12) in 90% yield. The alkynyl compounds 1 and 6 have been found to be active catalysts for the addition of triethylsilane to phenylacetylene. In all experiments, PhCH=CH2, PhC≡CSiEt3, cis-PhCH=CH(SiEt3), trans-PhCH=CH(SiEt3), and Ph(SiEt3)C=CH2 were obtained. On the basis of the results from the stoichiometric reactions together those from the catalytic experiments, reaction pathways for the formation of these silylate products are discussed.
