Rhodium(I)-mono- und -diazadienkomplexe, synthese, spektroskopische charakterisierung, oxidative additionsreaktionen und einsatz in der homogenen katalyse zur hydrosilylierung

α‐Dialdimine Complexes of Rhodium(I) and Iridium(I): Their Reactivity with Dioxygen and Dihydrogen

“…The 1 H NMR spectrum of 1 in C 6 D 6 shows two signals at δ = 8.97 and 7.67 ppm, which can be assigned to the protons of the backbone of the α‐dialdimine ligand. Similar chemical shifts have been reported for [Rh(Cl){ArN=C(H)C(H)=NAr}(CO)] (Ar = 2‐MeC 6 H 4 ; δ = 8.83 and 8.16 ppm in CDCl 3 ) 20. The 1 H NMR spectrum of 2 reveals resonances for the imine protons at δ = 8.67 and 7.43 ppm.…”

The mechanism of oxidative addition of Pd(0) to Si–H bonds: electronic effects, reaction mechanism, and hydrosilylation

“…[29][30][31][32] A key step in the mechanism of transition metal-catalysed hydrosilylation is the oxidative addition of the metal to the Si-H bond. [21][22][23]25,26,[33][34][35] While this fundamental step of organometallic chemistry, to form (silyl)M(H) complexes, has been well-studied for Pd's neighbouring elements Rh, [36][37][38][39][40][41][42][43][44][45][46][47][48] Pt, [49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64] and most other transition metals, [33][34][35] it is much less understood for Pd. The oxidative addition of Rh and Pt to Si-H is facile, and complexes have been reported with a variety of ligand scaffolds and silanes.…”

“…61 This uxional behaviour is also proposed for related Ni complexes. [89][90][91][92] A large variety of Rh complexes have been studied for oxidative addition with silanes, [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] and the mechanism has been elucidated in detail as well. 46 Elucidation of the details of the reaction mechanism is also relevant in the context of the oxidative addition of C-H bonds, since Si-H bonds oen react analogously; however, Si-H bonds are more basic and therefore more reactive with transition metals.…”

A New Series of Mono- and Dinuclear Hydridosilylrhodium(III) Complexes, RhCl(H)(SiAr3)L2and RhL(SiAr3)H(μ-Cl)(μ-H)RhH(SiAr3)L (L = P(i-Pr3)). Preparation by Oxidative Addition of HSiAr3and Molecular Structures of the Complexes

“…Silylrhodium complexes − have attracted increasing attention as possible intermediates of Rh-complex-catalyzed synthetic reactions, − including hydrosilylation of unsaturated molecules 16 and silylformylation of alkenes and alkynes . Recently, a pentacoordinated hydridosilylrhodium complex, RhCl(H)(SiR 3 )(DAD) (DAD = a Salen type diimine ligand), was reported to play an important role as the intermediate in hydrosilylation of alkenes catalyzed by RhCl(CO)(DAD) …”