STRUCTURE AND PROPERTIES OF DIESTERTIN(IV) COMPLEXES (CH3OOCCH2CH2)2SN(CH)CL (CH = DIMETHYLDITHIOCARBAMATE, DIHYDROBIS(PYRAZOLYL)BORATE)

Abstract

Diestertin(IV) complexes (CH3OOCCH2CH2)2Sn(Ch)Cl (1, Ch = dimethyldithiocarbamate (dtc); 2, Ch = dihydrobis(pyrazolyl)borate (bpb)) were prepared by reaction of the diestertin(IV) chloride with alkali-metal salts of the corresponding ligands, and their molecular structures were determined by X-ray analysis. The local geometry around the tin atom of 1 (P2(1)/n; a = 10.011 (1), b = 19.480 (2), c = 10.081 (2) angstrom; beta = 117.39 (1)-degrees; Z = 4; R = 0.0294) adopts a distorted trigonal bipyramid with the chelating dtc ligand whereas the geometry of 2 (Pbcn; a = 34.287 (4), b = 7.949 (2), c = 14.397 (2) angstrom; Z = 8; R = 0.0345) approximates to an octahedral arrangement owing to a weak intramolecular carbonyl oxygen-to-tin coordination of one ester group (Sn-O(1) = 2.745 (6) angstrom) in addition to the chelating bpb ligand. The reaction of 1 with sodium sulfide (CHCl3/H2O) in the mole ratio of 2:1 gives two different known diestertin(IV) complexes (CH3OOCCH2CH2)2Sn(S2CNMe2)2 and [(CH3OOCCH2CH2)2SnS]3. In contrast, the reaction of 2 with sodium sulfide does not give analogous chemical products but instead allows formation of a new zwitterionic species Hbpb, C6H9N4B (Pbcn; a = 15.177 (2), b = 7.397 (1), c = 14.207 (1) angstrom; Z = 8; R = 0.0368), along with the same trimeric sulfide.