Synthesis and structural characterization of two new main group element carboranylamidinates

Abstract

Two new main group element carboranylamidinates were synthesized using a bottom-up approach starting from o-carborane, ortho-C2B10H12 (1, = 1,2-dicarba-closo-dodecaborane). The first divalent germanium carboranylamidinate, GeCl[HLCy] (3, [HLCy]− = [o-C2B10H10C(NCy)(NHCy)]−, Cy = cyclohexyl), was synthesized by treatment of GeCl2(dioxane) with 1 equiv. of in situ-prepared Li[HLCy] (2a) in THF and isolated in 47% yield. In a similar manner, the first antimony(III) carboranylamidinate, SbCl2[HLiPr] (4, [HLiPr]− = [o-C2B10H10C(NiPr)(NHiPr)]−), was obtained from a reaction of SbCl3 with 1 equiv. of Li[HLiPr] in THF (56% yield). The title compounds were fully characterized by analytical and spectroscopic methods as well as single-crystal X-ray diffraction. Both compounds 3 and 4 are monomeric species in the solid state, and the molecular geometries are governed by a stereo-active lone pair at the metal centers.