STRUCTURAL ASPECTS OF TRANSITION METAL BENZENEDITHIOLATO COMPLEXES. Kristin Kirschbaum, Arnim Corbach, Arnold Feldmann, Klaus Laue, Dirk Pfeiffer and Dean M.Giolando, Department of Chemistry, University of Toledo, Toledo,Ohio, 43606-3390.
The coordination chemistry of transition metals containing a homoleptic thiolate environment is of general interest. We have been investigating the structural chemistry of complexes with 1,2-benzenedithiolato ligands. Three bis(l,2-benzenedithiolate)vanadyl complexes have been prepared: [N-n-Bu4]2[VO(S2C6H4)2] (la) monoclinic, P21/n, Z=4, a=15.579(4), b=14.229(3), c=23.401(4) Å, [[beta]]=103.77(1)deg., [HNEt3]2[VO(S2C6H4)2] (1b) monoclinic, P21/c, Z=4, a=8.236(1), b=25.560(3), c=13.637(3) Å, [[beta]]=98.16(1)deg., and [NEt4]2[VO(S2C6H4)2] (1c) monoclinic, P2/n, Z=4, a=18.540(3), b=9.141(3), c=18.970(4) Å, [[beta]]=93.21(2)deg.. Vanadyl complexes (1) are useful precursors to the homoleptic complex [NEt4]2[V(S2C6H4)3] (2) {orthorhombic, Pbca, Z=8, a=13.613(3), b=18.448(5), c=26.845(5) Å} . The six coordinate environment of 2 is comparable to those of [HNEt3]2[Mn(S2C6H4)3] (3) {tetragonal, P41212, Z=4, a=10.319(2), c=32.190(8) Å} and [Li]3[Cr(S2C6H4)3] (4) {orthorhombic, Pbcn, Z=4, a=15.788(3), b=22.046(4), c=13.092(3) Å} .