Stabilisation of Au-III and Au-I in the same complex molecule by a tridentate phosphinodithiolate ligand. Structures of [AuIIILC1] and [AuIL2AuIII] (L = {PhP(C6H3S-2-SiMe3-3)(2)}(2-))

The reaction of the organometallic complex [Au-III(damp-C-1,N) Cl-2] (damp- C,N- = dimethylaminomethylphenyl) with PhP(C6H3SH-2-SiMe3-3)(2), H2L, resul ts in cleavage of the Au-C bond and the formation of [(AuLCl)-L-III] and [( AuL2AuIII)-L-I] complexes. The square coordination environment of gold in [ AuLCl] is noticeably distorted (maximum deviation from planarity: 0.326(1) Angstrom) by the steric requirements of the tridentate chelating Ligand, bu t the oxidation state '+3' of the metal is retained. [(AuL2AuIII)-L-I] cont ains gold atoms in both square-planar (Au-III) and linear (Au-I) coordinati on environments. The square-planar Au-III is bound by two trans-chelated PS units, and the two remaining thiolate groups provide the linear coordinati on of Au-I. The Au-Au distance is 2.919(1) Angstrom, indicative of a weak b onding interaction. (C) 1998 Elsevier Science S.A. All rights reserved.