Synthesis, spectroscopy, and X-ray crystallographic analysis of (η3-dithiobenzoato-SCS′)oxo(trithioperoxybenzoato-S,S′S″)molybdenum(IV) and µ-oxo-bis[bis(dithiobenzoato-SS′)oxomolybdenum(V)]

Abstract

The title oxomolybdenum complexes [Mo^IVO(S₂CPh)(S₃CPh)] and [Mo^V₂O₃(S₂CPh)₄] have been obtained by the reaction of Na₂[MoO₄] with [NEt₂H₂][S₂CPh] in an acidic aqueous medium, followed by chromatographic separation on a silica column using carbon disulphide as eluant. They have been characterized by elemental analysis, i.r. and electronic spectroscopy. A single-crystal X-ray structure analysis of [Mo₂O₃(S₂CPh)₄] reveals a structure in which two Mo^VO(S₂CPh)₂ moieties are oxo-bridged. The monoclinic crystal, space group C2/c, has cell dimensions a= 38.951(9), b= 10.678(4), c= 16.777(3)Å, β= 111.28(1)°, and Z= 8. Block-diagonal least-squares refinement, based on 2 340 independent reflections with |F| > 3σ(F), yields an R factor of 0.070. An X-ray structure analysis of [MoO(S₂CPh)(S₃CPh)] has shown the presence of η³-dithiobenzoato- and trithioperoxybenzoato-ligands co-ordinated to oxomolybdenum(IV). The crystals are monoclinic, space group P2₁/c, with cell dimensions a= 15.614(2), b= 8.441(1), c= 13.125(2)Å, β= 104.46(1)°, and Z= 4. Least-squares refinement, based on 3 767 independent reflections with |F| > 3σ(F), yields an R factor of 0.035.