Carbon–Silicon Bond Activation by [Pd(ItBu)₂] – the Molecular Structures of [Pd(Me₃Si)(ItBu)(μ‐I)]₂ and [Pd(CH₂ItBu)I₂]

Abstract

The reaction of Me 3 SiCH 2 I with [Pd(ItBu) 2 ] (ItBu = 1,3-ditert-butyl-imidazol-2-ylidene) results, not in simple oxidative addition, but in carbon-silicon bond activation and formation of [Pd(Me 3 Si)(ItBu)(µ-I)] 2 (2) and [Pd(CH 2 ItBu)I 2 ] (3). The zwitterionic nature of the latter has been confirmed by DFT studies, and a possible mechanism for the formation of these

Rational Design of a Second Generation Catalyst for Preparation of Allylsilanes Using the Silyl-Heck Reaction

“…This compound is the first monomeric palladium complex resulting from oxidative addition of a silicon–halide bond to be characterized, and is also the first such complex to be supported by a phosphine ancillary ligand. 20 This complex was fully characterized in solution ( 1 H, 13 C and 31 P NMR in CD 2 Cl 2 at 0 °C), and the data are consistent with the structure shown in Figure 6 .…”

The key role of R–NHC coupling (R = C, H, heteroatom) and M–NHC bond cleavage in the evolution of M/NHC complexes and formation of catalytically active species

“… 122 Reaction of complex 42 with Me 3 SiCl affords compound 43 ( Scheme 9 ). 108 A similar adduct was detected by NMR in a C 6 D 6 solution of [Pd(I t Bu) 2 ] complex and Me 3 SiI after 40 day storage at room temperature; 175 the authors suggested that the NHC–SiMe 3 adduct was formed via Pd–NHC dissociation and subsequent reaction of the free NHC with Me 3 SiI. Facile reactions of PCl 3 , PBr 3 , SbCl 3 and AsCl 3 with Li/NHC adducts 44 afford the corresponding P–NHC, Sb–NHC and As–NHC products 45 ( Scheme 9 ).…”

Zwitterionic Palladium Complexes: Room-Temperature Suzuki–Miyaura Cross-Coupling of Sterically Hindered Substrates in an Aqueous Medium

“…Such kinds of complexes are also known in the literature. 44 Since the methylene proton in 1a is the most acidic proton, it is obvious that 2a should be formed easily. In fact, in the preparation of 2a, the zwittterion and the side product trans-PdCl 2 (py) 2 were formed exclusively even after prolonged heating at 80°C overnight, indicating that 2a is either kinetically stable or is indeed the thermodynamic product.…”