The Gas Phase Oxidation of Silyl Radicals by Molecular Oxygen: Kinetics and Mechanisms

Counterintuitive Chemistry: Carbene Stabilization of Zero-Oxidation State Main Group Species

“…For example, the 1:4 reaction of 28 with BH 3 ·THF in toluene resulted in the cleavage of the SiSi double bond, giving 34 in 72% yield (Scheme ). The highly reactive SiH 2 species has been observed as an intermediate in the chemical vapor deposition of silicon film via SiH 4 pyrolysis …”

“…90 The highly reactive SiH 2 species has been observed as an intermediate in the chemical vapor deposition of silicon film via SiH 4 pyrolysis. 91 34 represents the first "push−pull"-stabilized parent silylene (SiH 2 ), wherein the SiH 2 unit accepts one pair of electrons from the NHC ligand, while donating one electron pair to the NHC:Si(H)(B 3 H 7 )BH 2 moiety. In the presence of a small amount of free NHC ligand (28 to NHC = 5:1), the parallel reaction gives a mixture containing both 34 (30% yield) and 35 (28% yield) (Scheme 12).…”

Push–Pull Stabilization of Parent Monochlorosilylenes

“…The chemistry of silylenes (:SiR 2 ), silicon analogues of carbenes, has experienced impressive growth since the initial experimental observation of these transient divalent silicon species nearly half a century ago. − Since the seminal discovery of stable silylenes, such as :Si­(η 5 -C 5 Me 5 ) 2 and :Si­{N­( t Bu)­CH} 2 , ,, these species have evolved into potent ligands for synthesis of the corresponding transition metal complexes. − Furthermore, these compounds have attracted considerable attention due to their catalytic potential. , The parent silylene (:SiH 2 ) and chlorosilylenes [:SiCl 2 and :Si­(H)­Cl] − have been observed as reactive intermediates in chemical vapor deposition of silicon from silane (SiH 4 ) and chlorosilanes, respectively . However, the quest to stabilize these elusive silylenes under ambient conditions has long challenged chemists.…”