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

Abstract

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 reaction of [Au(PPh 3 )Cl] with the corresponding pyrimidine‐2‐thione in ethanol in the presence of triethylamine gave [Au(4,6‐Me 2 ,5‐EtpymS)(PPh 3 )] and [Au(4‐CF 3 pymS)(PPh 3 )] in good yields. The compounds were characterized by microanalysis, IR spectroscopy, FAB‐MS and, when sufficientlysoluble, 1 H, 13 C and 31 P NMR spectroscopy. Compounds [Cu 6 (4,6‐CF 3 PhpymS) 6 ] ( 1 ), [Ag 6 (4,6‐Me 2 ,5‐EtpymS) 6 ] · 2MeOH · 3H 2 O ( 2 ), [Cu 2 (4‐CF 3 pymS) 2 (dppm) 2 ] · 2CH 3 CN ( 3 ), [Cu(4‐CF 3 pymS)(PPh 3 ) 2 ] ( 4 ) and [Au(4‐CF 3 pymS)(PPh 3 )] ( 5 ) were also characterized by X‐ray diffraction.