Novel neutral hexacoordinate silicon(iv) complexes with two bidentate monoanionic benzamidinato ligands

Abstract

The novel neutral hexacoordinate bis(benzamidinato)silicon(iv) complexes 1-10 (SiN(4)X(2) skeletons; X = F, Cl, Br, C, N, S, Se) were synthesised and characterised by elemental analyses, single-crystal X-ray diffraction (except for 2) and NMR spectroscopy in the solid state and in solution. The dynamic behavior of 1 (SiN(4)Cl(2) skeleton) and 3 (SiN(4)F(2)) was additionally studied by variable-temperature NMR experiments. Compounds 1 and 2 (SiN(4)Br(2)) were obtained by reaction of SiCl(4) and SiBr(4), respectively, with two molar equivalents of the corresponding lithium amidinate. Compound 1 served as the starting material in the syntheses of 3-10, in which the two chloro ligands of 1 were substituted by two (pseudo)halogeno or one bidentate dianionic S,S, S,Se or Se,Se ligand. Compound 4 contains an SiN(4)C(2) skeleton and 5-7 contain an SiN(6) skeleton. With the preparation of 8 (SiN(4)S(2) skeleton), 9 (SiN(4)SSe) and 10 (SiN(4)Se(2)) it could be demonstrated that syntheses of hexacoordinate silicon(iv) complexes with soft chalcogeno ligand atoms are indeed feasible. Compounds 9 and 10 are the first hexacoordinate silicon(iv) complexes with Si-Se bonds.