Synthesis of heteroleptic gallium-substituted antimony hydrides by stepwise β-H elimination

Abstract

Heteroleptic stibanes Cp*(R)SbCl (R = Dip 1, N(SiMe₃)₂2, OB(NDipCH)₂3; Cp* = C₅Me₅; Dip = 2,6-i-Pr₂-C₆H₃) react with monovalent gallanediyl LGa (L = HC[C(Me)N(Dip)]₂) with elimination of 1,2,3,4-tetramethylfulvene, yielding heteroleptic metal-stabilized Sb hydrides [L(Cl)Ga](R)SbH (R = Dip 4, N(SiMe₃)₂5, OB(NDipCH)₂6). Compounds 1–6 were characterized by heteronuclear NMR (¹H, ¹¹B, ¹³C) and IR spectroscopy, and the solid-state structures of 4–6 were determined by single-crystal X-ray diffraction. A close correlation between the ¹H NMR chemical shift of the hydride ligand and the electronegativity of the Sb-coordinating atoms was revealed.