Mechanistic Studies of Palladium(II)-Catalyzed Hydrosilation and Dehydrogenative Silation Reactions
作者:Anne M. LaPointe、Francis C. Rix、Maurice Brookhart
DOI:10.1021/ja962979n
日期:1997.2.1
cationic Pd(II) complexes, [(phen)Pd(CH3)(L)]+[BAr‘4]- phen = 1,10−phenanthroline; L = Et2O, Me3SiC⋮CSiMe3; Ar‘ = 3,5-(CF3)2C6H3) catalyze the hydrosilation and dehydrogenative silation of olefins. Hydrosilation of ethylene, tert-butylethylene, 1-hexene, and cyclohexene by HSiR3 (R = CH2CH3, C6H5) occurs in the presence of 1 mol % [(phen)Pd(CH3)(L)]+[BAr‘4]-. The reaction of tert-butylethylene with HSi(i-Pr)3
ADC-metal complexes as effective catalysts for hydrosilylation of alkynes
作者:Bruno G.M. Rocha、Elena A. Valishina、Rogério S. Chay、M. Fátima C. Guedes da Silva、Tatyana M. Buslaeva、Armando J.L. Pombeiro、Vadim Yu. Kukushkin、Konstantin V. Luzyanin
DOI:10.1016/j.jcat.2013.09.003
日期:2014.1
Aminocarbene complexes cis-[PtCl2C(N(H)N = (CRR3)-R-2)=N(H)R-1)(CNR1)] (7-15) prepared via the nucleophilic addition of hydrazones H2N-N=CR2123 [R-2, R-3 = Ph 4; R-2/123 = 9H-fluorenyl 5; R-2 = H, R-3 = 2-(OH)C6H4 6] to cis-[PtCl2(CNR1)2] [R1 = cyclohexyl (Cy) 1, 2,6-Me2C6H3 (Xyl) 2, 2-CI-6-MeC(6)H(3)3] were evaluated as catalysts for the hydrosilylation of terminal allcynes with trisubstituted silanes giving vinyl silanes. The optimized catalytic system runs at 80-100 degrees C in dry toluene for 3-6 h with a typical catalyst loading of 0.1 mol%. A range of substrates with different steric hindrance and activity (Et3SiH, Pr3SiH, (Pr3SiH)-Pr-i, and PhMe2SiH as silanes; PhC CH, (BuC)-Bu-t CH, and 4-(Bu-t)C6H4 CH as allcynes) were successfully transformed into the target silylated products in 83-99% yields attesting the versatility of our catalytic system. Decreasing the catalysts loading to 10-3 mol% guaranteed the maximum TONs of 4.0 x 10(4) and TOFs of 1.7 x 10(2) (h(-1)) that were accomplished within 24 h of the reaction. (C) 2013 Elsevier Inc. All rights reserved.
Hydrosilylation of monosubstituted acetylenes in the presence of platinum(II) complexes
作者:V. B. Pukharevich、I. I. Tsykhanskaya、N. I. Ushakova、M. I. Gel'fman、M. G. Voronkov
DOI:10.1007/bf00960278
日期:1984.12
Tanke, Robin S.; Crabtree, Robert H., Journal of the American Chemical Society, 1990, vol. 112, # 22, p. 7984 - 7989