title: Versatile ligand behavior of hydrotris(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate. Syntheses and crystal structures of Cu(I) and Bi(III) complexes.
abstract: Preparations of copper(I) and bismuth(III) complexes of hydrotris(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate (Tr(Et,Me)) are described. These complexes have been characterized by means of spectroscopy and microanalysis. Molecular structures of [Cu(Tr(Et,Me))](2) x 2.5CH(3)CN x 0.5H(2)O (3a) and [Bi(Tr(Et,Me))(2)]NO(3) x 2CHCl(3) (4a) have been determined by single-crystal X-ray diffraction. In the centrosymmetric dimeric copper(I) complex, Tr(Et,Me) acts in the k(3)S,S',H:kS' ' coordination mode. The metal is found in a distorted trigonal geometry as the ligand exhibits an "S(3)-inverted" conformation at the boron center so that a weak [B-H.Cu] agostic interaction renders the overall coordination of the (3 + 1) type. On the other hand, in the bismuth complex, Tr(Et,Me) presents the k(3)S,S',S' ' coordination mode and the "S(3)-normal" conformation. The metal is found in a regular octahedral geometry bound by six thioxo groups of two ligands. Species distributions in solution have been studied using electrospray ionization mass spectrometry upon dissolution of 3a and 4a crystals in acetonitrile. Monomeric and polynuclear copper(I) complexes with different M:L ratios are present in solution, while for 4a only the monomeric species is present.
authors.affiliation: Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Università degli Studi di Parma, Parco Area delle Scienze 17a, I 43100 Parma, Italy.
authors.forename: Maria
authors.initials: M
authors.lastname: Careri
authors.forename: Lisa
authors.initials: L
authors.lastname: Elviri
authors.forename: Maurizio
authors.initials: M
authors.lastname: Lanfranchi
authors.forename: Luciano
authors.initials: L
authors.lastname: Marchiò
authors.forename: Clara
authors.initials: C
authors.lastname: Mora
authors.forename: Maria Angela
authors.initials: MA
authors.lastname: Pellinghelli