Reactivity of O,N-heterocyclic germylene and stannylene towards μ-dithio-bis(tricarbonyliron)

Abstract

Synthesis and single-crystal X-ray diffraction study (SC-XRD) of the O,N-heterocyclic germylene Ge(PhAp) (1) containing chelate 4,6-di-tert-butyl-N-phenyl-o-amidophenolate ligand (PhApH2, where Ap – o-amidophenolate) are reported. Germylene 1 demonstrates a monomeric structure in contrast to earlier known related stannylene Sn(PhAp) (2) existing as a dimer. Diverse weak intermolecular interactions (Ge…Ge, CH…π(chelate) and Ge…π(arene)) were detected in the crystal packing of germylene 1. Hirshfeld surface analysis has been performed to evaluate such interactions. Reactivity of compounds 1 and 2 towards dithiodiiron hexacarbonyl has been examined. Low-valent germanium(II) and tin(II) centers are readily inserted into S-S bond of dithiodiiron hexacarbonyl with the formation of Fe4(µ4-ES4)(CO)12 (E: Ge(3); Sn(4)) and bis-ligand complexes of tetravalent metals E(PhAp)2. The resulting germanium(IV) and tin(IV) bis-o-amidophenolates were isolated as six-coordinated pyridine adducts E(PhAp)2(Py)2 (E: Ge(5); Sn(6)). All complexes were characterized by SC-XRD.