Four novel mononuclear and polynuclear Cu(I) thiosaccharinates with triphenylphosphane and bis(diphenylposphino)methane. synthesis and structural study of Cu4(tsac)4(PPh3)3, Cu(tsac)(PPh3)2, Cu4(tsac)4(dppm)2, and Cu2(tsac)2(dppm)2.

DENNEHY MARIANA; GABRIELA P. TELLERIA; OSCAR V. QUINZANI; GUSTAVO A. ECHEVERRIA; OSCAR E. PIRO; EDUARDO E. CASTELLANO

INORGANICA CHIMICA ACTA

ELSEVIER SCIENCE SA

Año: 2009 vol. 362 p. 2900 - 2908

0020-1693

Four new ternary complexes of copper(I) with thiosaccharin and phosphanes were prepared. The reactionof [Cu4(tsac)4(CH3CN)2] (1) (tsac: thiosaccharinate anion) with PPh3 in molar ratios Cu(I)/PPh3 1:075 and1:2 gave the complexes [Cu4(tsac)4(PPh3)3]  CH3CN (2) and Cu(tsac)(PPh3)2 (3), respectively. The reactionof 1 with Ph2PCH2PPh2 (dppm) in molar ratios Cu(I)/dppm 2:1 and 1:1 gave the complexes [Cu4(tsac)4(dppm)2]  2CH2Cl2 (4) and [Cu2(tsac)2(dppm)2]  CH2Cl2 (5), respectively. All the compounds havebeen characterized by spectroscopic and X-ray crystallographic methods.Complex 2 presents a tetra-nuclear arrangement with three metal centers in distorted tetrahedral S2NPenvironments, the fourth one with the Cu(I) ion in a distorted trigonal S2N coordination sphere, and thetsac anions acting as six electron donor ligands in l3-S2N coordination forms. Complex 3 shows mononuclearmolecular units with copper(I) in a distorted trigonal planar coordination sphere, built withthe exocyclic S atom of a mono-coordinated thiosaccharinate anion and two P-atoms of triphenylphosphanemolecules. With dppm as secondary ligand the structures of the complexes depends strongly onthe stoicheometry of the preparation reaction. Complex 4 has a centrosymmetric structure. Two triplybridged Cu2(tsac)2(dppm) units are joined together by the exocyclic S-atoms of two tsac anions actingeffectively as bridging tridentate ligands. Complex 5 is conformed by asymmetric dinuclear moietieswhere the two dppm and one tsac ligands bridge two Cu(I) atoms and the second tsac anion binds oneof the metal centers through its exocyclic S-atom.