14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes

Abstract

Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh(III) devoid of agostic interactions. The complexes [X-Rh(κ3(P,Si,Si)PhP(o-C6H4CH2SiiPr2)2], where X = Cl (Rh-1),...

PtII−N‐Heterocyclic Carbene Complexes in Solvent‐Free Alkene Hydrosilylation

“…13 C NMR (101 MHz, CDCl 3 ): δ (ppm)=33.1, 31.8, 23.2, 22.8, 17.8, 14.3, 2.0, −0.1. Analytical data match the values reported in the literature [26] …”

“…Analytical data match the values reported in the literature. [26] 1,1,1,3,5,5,5-heptamethyl-3-octyltrisiloxane (6 ab) CAS 17955-88-3: Following the general procedure (B), 6 ab was obtained as a colorless oil (664 mg, 99 %). 1 H NMR (300 MHz, CDCl 3 ): δ (ppm) = 1.38-1.17 (m, 12H), 0.88 (t, J = 6.6 Hz, 3H), 0.45 (t, J = 7.7 Hz, 2H), 0.09 (s, 18H), 0.01 (s, 3H).…”

Catalytic activation of remote alkenes through silyl-rhodium(iii) complexes

“…41 However, this catalytic system shows quite good activity compared to others found in the literature, which require higher catalyst loadings or higher temperatures. 20–27…”

“…41 However, this catalytic system shows quite good activity compared to others found in the literature, which require higher catalyst loadings or higher temperatures. [20][21][22][23][24][25][26][27] To complete this study, the hydrosilylation of other alkenes with 2-L2 was studied (Table 4). First, unisomerizable terminal alkenes, such as α-methylstyrene, 1,1-diphenylethylene and tert-butylethylene (tbe), were tested under standard conditions.…”

Cyclobutadiene platinum complex as a new type of precatalyst for hydrosilylation of alkenes and alkynes

“…The products of Markovnikov‐type addition were not detected in the NMR spectra of crude mixtures, but small amounts of vinylsilanes 2 (1–11%) were observed as typical by‐products. [ 37 ] The cyclobutadiene catalyst 1 tolerated nitrogen, sulfur, and oxygen functional groups in the olefin substrates giving corresponding products 3f – 3h . Interestingly, N , N ‐diethylallylamine gave the hydrosilylation product 3f in almost quantitative yield, while the unsubstituted allylamine was far less active at the ambient temperature (16% yield of 3i ).…”