Reactivity of the metal-silicon bond in organometallic chemistry

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

“…In fact, only a few stable complexes containing a Pd-Si bond have been isolated, particularly in the case of non-chelating systems. [9] [Pd(SiCl 3 ) 2 -(PPh 3 ) 2 ] has been obtained by the reaction of Pd(PPh 3 ) 4 with HSiCl 3 or Cl 3 SiSiCl 3 , and stable bis(silyl)palladium(II) complexes have been synthesised by the reaction of Pd 0 or Pd II triphenylphosphane complexes with chelating hydrosilanes.…”

“…[3] The studies conducted in this field have allowed a comparison with related systems containing a metal-carbon bond and provided a better understanding of the elementary steps in important industrial catalytic reactions, such as hydrosilylation, [4] dehydrogenative couplings of primary or secondary silanes, [5] silylformylation, [6] preparation of polysilanes [7] and bissilylation. [8] Silylpalladium complexes are believed to be key intermediates in a number of such Pd-catalysed transformations, and the limited stability and the high reactivity of the Si-Pd bond in these compounds is believed to be responsible for their high catalytic activity.…”

Silicometallics and catalysis

“…36,37 Inactivity of metallacarbene initiators in productive homometathesis of vinylsilanes is accounted for by steric effects and a relative stability of the silyl-substituted carbenes bonded to the metal. 38 However, the successful crossmetathesis of vinyl-substituted silsesquioxanes with alkenes, 39 and above all our recent experiments on the efficient cross-metathesis of vinyltrialkoxysilanes and vinyltrisiloxysilanes with styrene 40 -all occurring in the presence of ruthenium carbenes-may be the proper route for finding circumstances for generalization of the reaction which proceeds according to Eqn [5].…”

“…Numerous developments have been the subject of comprehensive reviews in synthetic, stoichiometric and catalytic chemistry of metalsilicon bonding in recent years. [3][4][5][6] Therefore, although in catalytic conversions of (organo)silicon compounds only hydrosilylation reactions are well known as processes of industrial importance, 7-10 since 1985 other reactions of silicon compounds catalyzed by transition-metal complexes have been revealed and spectacularly developed. Most of them occur via a mechanism involving metal-silicon and metal-hydrogen bonds, only occasionally accompanied (or sided) by metal-carbon bonds.…”

New complexes with MSiO or MSiS linkages (M=Fe or Co)

“…In contrast, species such as (MeO) 3 SiCo(CO) 4 are apparently readily handled [10]. Braunstein [11] has developed extensive chemistry of bi-metallic compounds based on (MeO) 3 Si groups acting as bridging ligands. More recently, stable metallosilanol and metallosiloxane compounds have been reported, including derivatives (Me 5 C 5 )(PMe 3 )(OC) 2 MSiR 2 (OH) (M = Cr, Mo, W) from Malisch's group [12], and osmium examples from Roper's laboratory [13].…”