10536-67-1Relevant academic research and scientific papers
Hydrodealkoxylation reactions of silyl ligands at platinum: Reactivity of SiH3 and SiH2Me complexes
Mitzenheim, Cathérine,Braun, Thomas,Laubenstein, Reik,Braun, Beatrice,Herrmann, Roy
, p. 6394 - 6404 (2016/05/09)
The platinum(ii) complex [Pt(H)2(dcpe)] (1; dcpe = 1,2-bis(dicyclohexylphosphino)ethane) reacts with an excess of the dialkoxymethylsilanes (HSiMe(OR)2; R = Me, Et) to give the bis(silyl) complex [Pt(SiH2Me)2(dcpe)] (3) and trialkoxymethylsilanes by hydrodealkoxylation reactions. These rearrangements of the silyl ligands involve Si-O bond activations. The exchange of the alkoxy moieties against silicon-bound hydrogen atoms occurs stepwise. The intermediate complexes [Pt(H){SiMe(OEt)2}(dcpe)] (5), [Pt{SiMe(OEt)2}2(dcpe)] (6), [Pt{SiHMe(OEt)}2(dcpe)] (7) and [Pt{SiHMe(OMe)}2(dcpe)] (8) were detected. Treatment of the complex 1 with an excess of dichloromethylsilane yields the bis(silyl) complex [Pt(SiMeCl2)2(dcpe)] (9). The hydrido silyl complex [Pt(H)(SiMeCl2)(dcpe)] (10) was identified as an intermediate. The reactions of the complexes [Pt(SiH3)2(dcpe)] (2) and [Pt(SiH2Me)2(dcpe)] (3) with iodomethane lead to a transfer of the SiH3 and SiH2Me ligands. Methylsilane and dimethylsilane, respectively, as well as the platinum diiodo complex [Pt(I)2(dcpe)] (11) were identified as main products.
Proton Affinity and Heat of Formation of Silylene
Shin, Seung Koo,Beauchamp, J. L.
, p. 1507 - 1509 (2007/10/02)
Using the techniques of Fourier transform ion cyclotron resonance spectroscopy, we determined the proton affinity of silylene to be 201 +/- 3 kcal*mol-1 from a study of the kinetics and thermochemistry of proton transfer from SiH3+ to a series of n-donor bases with well-established gas-phase base strengths.This value leads to ΔHfo298(SiH2) = 69 +/- 3 kcal*mol-1, which is 11 kcal*mol-1 higher than the previously accepted value (Wals, R.Acc.Chem.Res. 1981, 14, 246-252), but in excellent agreement with the recent theoretically recommended value of 68.1 kcal*mol-1 (Ho, P.; Coltrin, M.E.; Binkely, J.S.; Melius, C.F.J.Phys.Chem. 1985, 89, 4647-4654).
