The compounds M(SOCPh),, (M = Pb, n = 2; M = Bi, n = 3) have been prepared by the reaction of M(OAc), or M(SPh), with a slight excess of PhCOSH in MeOH. The ligands PhCOS-, (c-C6Hl1),PCS2 and (c-C6HI,),PO solubilize Pb(SOCPh), in solvents in which it is otherwise poorly soluble. Neither Ph,P nor Ph,P increase the solubility of Pb(SOCPh), and none of the above five ligands enhance the solubility of very poorly soluble Bi(SOCPh),. Solubilization of the Pb(I1) compound is due in each case to a 1: 1 reaction as shown by the isolation of (Ph,As)(SOCPh),] (1) and Pb(SOCPh),(S,CP(c-C6Hll 1, ) (2), and by a multi-NMR (,'P, ,07pb) study of the system Pb(S0CPh) : (c-C6Hl ,),PO (in which unidentified more ligand-rich species are also formed). 1 and 2 have been characterized by multi-nuclear magnetic resonance spectroscopy (I3c, ,IP, ,07pb, as appropriate) and by single crystal X-ray diffractometry techniques at -50°C. The compound l.CH,Cl, (= 1') crystallizes in the triclinic space group P i with Z = 2. The c stal data for 1' are a = 13.395 (4) (3)) g cM3, RF = 0.034, R,, = 0.029. The (c-C6Hl1),PCS, ligand binds in an anisobidentate manner and the primary coordination geometry around Pb in the neutra) molecule is trigonal pyramidal, the primary Pb-S distances in the PbS, kernel being 2.626(2), 2.755(2), and 2.885(2) A. The weakly bound sulfur of the (c-C6H,,),PCS, acts as a bridge, again producing a centrosymmetric dimer. In addition to the two weak inLeractions to sulfur