METAL-OXYGEN VERSUS METAL-SULFUR BONDING OF THE AMBIDENT MONOTHIOPHOSPHINATO LIGAND IN SOME TRIPHENYLMETAL(IV) DERIVATIVES, PH(3)M[OSPR(2)](M=GE,SN,PB) - CRYSTAL-STRUCTURES OF PH(3)GE[O(S)PPH(2)] AND [PH(2)SN(O(S)PPH(2)) (MU-OH)](2)

Diorganomonothiophosphinato-triphenylmetal(IV) derivatives, Ph(3)M(OSP R(2)) (M = Ge, Sn, Pb; R = Me, Et, Ph), were prepared and investigated . The IR and multinuclear (H-1, C-13, P-31) NMR spectra are discussed in relation to the M-O and/or M-S bonding of the ambident OSPR(2)(-) l igand. The crystal and molecular structures of Ph(3)Ge[O(S)PPh(2)] (1) and [Ph(2)Sn{O(S)PPh(2)}(mu-OH)](2) (2) were determined by X-ray diff ractometry. The asymmetric unit for Ph(3)Ge[O(S)PPh(2)] contains two i ndependent molecules. The monothiophosphinato group is bonded to germa nium only through oxygen (av. Ge-O 1.826, Ge ... S 3.892 Angstrom), le ading to a tetrahedral coordination around the germanium atom. The cry stal [Ph(2)Sn{O(S)PPh(2)}(mu-OH)](2) consists of dimeric units built u p through Sn-O-Sn bridges involving the oxygen atom of the hydroxy gro ups. The monothiophosphinato group is again monodentate [Sn(1)-O(1) 2. 089(3), Sn(1)... S(1) (non-bonding) 4.164 Angstrom] and the coordinati on geometry around tin is trigonal bipyramidal, with the O(1) atom of the phosphorous ligand and the O(2') atom of a bridging hydroxy group in axial positions. Copyright (C) 1996 Elsevier Science Ltd