Synthesis and Structural Characterization of Copper(I), Silver(I) and Gold(I) Complexes with Pyrimidine‐2‐thionato Ligands and their Adducts with Phosphanes

Abstract

Homoleptic copper and silver compounds of a series of pyrimidine-2-thionato derivatives (RpymS -; R = 4,6-Me 2 ,5-Et; 4-CF 3 ; 4,6-CF 3 ,Ph) have been synthesized by electrochemical oxidation of anodic metal (copper or silver) in a cell containing an acetonitrile solution of the appropriate thione and a small amount of tetraethylammonium perchlorate as electrolytic carrier. Subsequent reaction of these pyrimidine-2-thionato compounds with triphenylphosphane or bis(diphenylphosphanyl)methane (dppm) in acetonitrile allowed the synthesis of the corresponding heteroleptic complexes. The

The use of sacrificial anodes for the electrochemical synthesis of metallic complexes

“…In the electrolysis of acetonitrile solutions containing soft donor proligands with copper anodes, this low oxidation state is kept in the final complex; and so was it for the synthesis of the complex with the N,S donor ligand such as pyrimidine (HL1) and pyridine-2-thione (HL2) derivatives; i. e. [Cu 6 (L1d) 6 ] showed a paddle-wheel structure (Fig. 2, right), with the thionato ligands acting as trinuclear triple bridges [36].…”

“…The crystal structures of all these complexes contain neutral hexanuclear units which can be described as paddle wheel structured; the ligands exhibit a monoanionic trinuclear triple bridging behavior as it can be seen inFig. 2, right, for a representative compound, [Cu 6 (L1d) 6 ][36].A higher steric hindrance can modify the structure by reducing the nuclearity of the complexes but keeping the same coordination mode for the ligand, as reported for Cu(I) complexes containing ligands with bulky substituents located near the donor atoms like 3-trimethylsilylpyridine-2-thionato [L2d] [275]. The electrochemical synthesis yielded a…”

“…These heteroleptic complexes with phosphanes were obtained by reaction between the electrochemically synthesized complex and the appropriate phosphane [36,254,270,271,274,276]. consists of polymeric chains with the monoanionic thionato ligands acting as binuclear triple bridges.…”

(4,6-Dimethyl-2-sulfanylidenepyrimidin-1-ium) trichlorido(thiourea-κS)zinc(II)

“…Substituted pyrimidine-2-thiols, which possess both nitrogen and sulfur potential coordination sites, have been widely used in the preparation of traditional metal complexes and their coordination modes have been thoroughly investigated. In most cases, they are found as the anion and coordinate to metal centres through both S and N atoms (see, for example, Rodríguez et al, 2011). Other coordination modes are found more rarely.…”

A three-dimensional metal–organic polymer: poly[bis(μ2-pyrimidine-2-thiolato-κ4N1,S:S,N3)lead(II)]

“…Complexes that contain only Spym À and substituted derivatives in the coordination sphere of many transition metal ions were obtained as mononuclear structures. Hexanuclear complexes were obtained with Cu I and Ag I (Castro et al, 1992;Ramaprabhu et al, 1994;Kitagawa et al, 1992;Rodríguez et al, 2011;Li et al, 2013). Only a few compounds of p-block ions are known, i.e.…”