Mononuclear and binuclear Cu(I) complexes with metal-sulfur ligation

Structural and Spectroscopic Properties of New Copper(I) Complexes with 1,1,1‐Tris(diphenylphosphanylmethyl)ethane and Heterocyclic Thiolates

“…On the other hand, each deprotonated thione ligand is bonded to the metal center in 1 and 2 with a "short" Cu-S bond length of 2.2669(6) and 2.2570(7) Å respectively, which is far from the values normally observed in other tetrahedral Cu I complexes bearing neutral pyridine-2-thione or pyrimidine-2-thione, but also from the value of 2.302(4) Å observed for [CuBr(κ 1 -py2S)(PPh 3 ) 2 ] bearing the heterocyclic thione ligand also in its deprotonated form. [13] …”

An Experimental and Theoretical (DFT) Investigation of the Coordination Mode of 2,4‐Dithiouracil (2,4‐dtucH2) in Copper(I) Complexes with1,2‐Bis(diphenylphosphanyl)benzene (dppbz): The Crystal Structures of [Cu(μ‐Br)(dppbz)]2 and [CuBr(dppbz)(2,4‐dtucH2)]

“…During the reaction of 2,4-dtucH 2 with CuBr, a small quantity of greenish yellow crystals was separated at the initial stages of the evaporation of the diluted acetonitrile mother liquid; their analytical and spectroscopic data were identical to those of the [CuBr(dppbz)] intermediate. In this way we were able to characterise the intermediate by X-ray crystallography as the thione-free dimer [CuBr(dppbz)] 2 (3). It should be noted that 3 is inert in the reactions with a number of heterocyclic thiones [e.g.…”

“…Along these lines a wealth of complexes exhibiting variable nuclearities and often unusual geometries have been synthesised and studied so far. [1][2][3][4][5][6][7] A large number of mixed-ligand complexes of the univalent coinage metals, particularly those of Cu I , incorporating tertiary arylphosphanes as a second, bulky soft donor ligand have been thoroughly investigated in an attempt to understand the factors that may affect the stoichiometric and geometrical preferences [a] Aristotle University of Thessaloniki, Faculty of Chemistry, Inorganic Chemistry Laboratory,334 ties of the model complexes [Cu(μ-X)(dppbz)] 2 and [CuX(dppbz) (2,4-dtucH 2 )] (X = Cl, Br, or I) are adequately described by DFT/B3LYP computational techniques. All model dinuclear [Cu(μ-X)(dppbz)] 2 complexes exhibit π-type MOs delocalised over the entire four-membered Cu(μ-X) 2 Cu ring, thereby accounting for the near equivalency of the Cu-X bonds.…”

“…(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) of these compounds. [3] In this context, some examples of three-coordinate Cu I complexes, where the steric requirements of the phosphane ligands exert an influence on the coordination number, have also been reported. [4] Moreover, a number of halo-or thione-S-bridged dinuclear mixed-ligand complexes have been synthesised and structurally well characterised.…”

“…[4] Moreover, a number of halo-or thione-S-bridged dinuclear mixed-ligand complexes have been synthesised and structurally well characterised. [3,5] In contrast to the monodentate triarylphosphanes, didentate P-donor ligands, especially the oligomethylene-backboned symmetric diphosphanes formulated as Ph 2 P(CH 2 ) n PPh 2 (n = 1, 2 or 4), favour the formation of dinuclear complexes. [6] On the other hand, the rigid cis-1,2-bis(diphenylphosphanyl)ethane (cis-dppen) and 1, 3-bis(diphenylphosphanyl)propane (dppp) have been found to chelate at a single metal centre, yielding mononuclear pseudotetrahedral Cu I species.…”