Reactivity of Silylene with Gallium‐ and Boron Trihalide at Reductive Conditions Resulting in Unforeseen Products

Abstract

Herein, we report a one-pot reaction of gallium and boron halides with potassium graphite in the presence of benzamidinate stabilized silylene LSi-R, (L = PhC(N t Bu) 2 ). The reaction of LSiCl with an equivalent amount of GaI 3 in the presence of KC 8 leads to the direct substitution of one chloride group by gallium diiodide simultaneously additional coordination of silylene resulted in L(Cl)Si!GaI 2 -Si(L)!GaI 3 (1). In compound 1, the structure comprises two differently coordinated gallium atoms where one gallium presents between two silylenes and the other gallium is only coordinated by one silylene. In this Lewis acid-base reaction the oxidation states of the starting materials remain unchanged. The same is valid in the silylene boron adduct formation of L( t Bu)Si-BPhCl 2 (2) and L( t Bu)Si-BBr 3 (3). This new route provides access to galliumhalosilanes challenging to synthesize by any other method.

A Neutral Borylene and its Conversion to a Radical by Selective Hydrogen Transfer

“…Fascinated by these findings, we were interested to synthesize a five-membered C 2 PBSi ring containing Si­(II) and B­(I) in the form of a radical cation, radical, and borylene to study its ability in H-abstraction reactions. Strong σ-donor and π-acceptor properties of cyclic alkyl­(amino) carbenes (cAACs) ,− and σ-donor properties of amidinate silylenes , have been judiciously exploited for the stabilization of various radicals, radical cations, and radical anions of p-block elements.…”

Synthesis and Characterization of Substituted Phosphasilenes and its Rare Homologue Stibasilene >Si=Sb−

“…Such lack of isolable stiba‐ and bismasilenes provoked us to challenge the preparation of a doubly bonded heavy analogues R 2 Si=Ear (E=P, Sb, Bi), of the Schiff base derivatives. Surprisingly the reactivity of amidinate stabilized silylene towards antimony‐based compound remained almost unexplored [10b–h] . Which embarked us to synthesize phosphasilenes >Si=P− and its heavy homologue stibasilene >Si=Sb− using advantage of the above‐described unified synthetic approach, unfortunately could not obtained the bismasilenes.…”