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 [MoIVO(S2CPh)(S3CPh)] and [MoV2O3(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 MoVO(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.