Synthesis and structures of gallaarsenes LGaAsGa(X)L featuring a Ga–As double bond

Abstract

Three equivalents of LGa {L = HC[C(Me)N(2,6-i-Pr₂C₆H₃)]₂} react with AsX₃ (X = Cl, Br) by insertion into two As–X bonds, followed by the elimination of LGaX₂ and formation of LGaAsGa(Cl)L (1) and LGaAsGa(Br)L (2). According to single crystal X-ray analysis, 1 and 2 each exhibit one Ga–As single bond and one Ga–As double bond. The π-bonding contribution (9.71 kcal mol⁻¹1 and 9.44 kcal mol⁻¹2) was proved by variable temperature (VT) ¹H NMR spectroscopy, while the electronic structure of 1′ was studied by quantum chemical calculations.