ChemInform Abstract: REAKTION VON SILBER(I)‐ UND QUECKSILBER(II)‐SALZEN MIT KALIUMBENZOLTHIOSULFONAT

Gundorina, A. A.; Sergeeva, A. N.

doi:10.1002/chin.197515397

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“…The monothiosulfonato-Cu(I) complexes (CuMeS 2 O 2 , CuEtS 2 O 2 , and CuPrS 2 O 2 ) were, however, obtained via reduction of copper(II) by thiosulfonates. 18,19 In an extension of our previous work, in which a series of thiosulfate complexes were stabilized through the use of the tripodal tetradentate ligand tris(2-aminoethyl)amine (tren) and several N-functionalized derivatives of tren, 3 we present herein the first detailed investigation of copper(II) thiosulfonate complexes. We report the syntheses, characterization, and X-ray crystal structures of three copper(II) complexes of composition [Cu(Me 3 tren)(RS 2 O 2 )](ClO 4 ), where Me 3 tren ) tris(2-methylaminoethyl)amine and R ) Me, Ph, and MePh, and compare structural features of these complexes, for example, intramolecular hydrogen bonding, with those of thiosulfate copper(II) complexes bearing these tripodal polyamine ligands.…”

Section: Introductionmentioning

confidence: 96%

“…The coordination chemistry of thiosulfonates has not been extensively studied. The limited examples of thiosulfonate−metal complexes include Au(I), − Cu(I), , Fe(II), Ru(II), , Ag(I), Hg(II), Pt(II), , and Ir(III) complexes. To our knowledge there have not been any quantitative studies on the formation of Cu(II) thiosulfonates complexes.…”

Section: Introductionmentioning

confidence: 99%

“…To our knowledge there have not been any quantitative studies on the formation of Cu(II) thiosulfonates complexes. The monothiosulfonato−Cu(I) complexes (CuMeS 2 O 2 , CuEtS 2 O 2 , and CuPrS 2 O 2 ) were, however, obtained via reduction of copper(II) by thiosulfonates. , …”

Section: Introductionmentioning

confidence: 99%

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Stabilization of Copper(II) Thiosulfonate Coordination Complexes Through Cooperative Hydrogen Bonding Interactions

Fischmann¹,

Forsyth²,

Spiccia³

2008

Inorg. Chem.

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A series of copper(II) thiosulfonate complexes have been prepared via the reaction of [Cu(Me 3tren)(OH 2)](ClO 4) 2 (Me 3tren = tris(2-methylaminoethyl)amine) with three thiosulfonate ligands (RSO 2S (-), where R = Me, Ph, and MePh) and characterized by microanalysis, FTIR spectroscopy, and X-ray crystallography. In these complexes, the distorted trigonal bipyramidal copper(II) coordination sphere is occupied by four amine nitrogen atoms from the tripodal tetramine ligand and an apically bound sulfur atom from the thiosulfonate ligand. By using the tripodal tetramine ligand the oxidation of the thiosulfonate has been restricted, allowing the isolation of the complexes. The Cu-S distances were found to be similar to those in related thiosulfate complexes, indicating coordinative interactions of similar strength. Two types of intramolecular hydrogen bonding interactions were evident which enhance the binding of the thiosulfonate to the copper(II) center. These interactions, which involve two amine N-H groups and either one or two thiosulfonate oxygens, were found to be weaker than in the corresponding thiosulfate complexes. The complex formation constants for the thiosulfonate complexes (log K f = 0.3-0.7) were found to be two orders of magnitude lower than compared to the thiosulfate analogues. This correlates well with a lower strength of intramolecular hydrogen bonding.

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Section: Introductionmentioning

confidence: 96%