Dithiocarbamate copper(I) and silver(I) complexes: Synthesis, structure and thermal behavior

Abstract Complexes [M(PBu 3 ) n (S 2 CNRR′)] (M = Cu, Ag; n  = 1, 2, 3; R = R′ = CH 2 CH CH 2 , (CH 2 ) 4 , C 2 H 4 OH; R = Me, R′ = C 2 H 4 OH; R = Bu, R′ = C 2 H 4 OH) ( 4 – 9 ) are accessible by the reaction of [Cu(PBu 3 ) n Cl] ( 1a – c ) or [Ag(PBu 3 ) n (NO 3 )] ( 2a – c ) with [K(S 2 CNRR′)] ( 3a – e ). The respective silver(I) dithiocarbamates 7 – 9 and [Ag(PPh 3 ) 2 (S 2 CNRR′)] ( 12a , R = Me; 12b , R = Bu) could be synthesized by the subsequent treatment of 3 with [AgNO 3 ] ( 10 ) giving [AgS 2 CNRR′] ( 11 ) followed by addition of n equivalents of the phosphine L (L = PBu 3 , PPh 3 ). Exemplary, the 31 P{ 1 H} NMR spectra of [Ag(PBu 3 ) n (S 2 CNMe(C 2 H 4 OH)] ( n  = 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5) were investigated in the temperature range of 308–178 K showing phosphine ligand exchange processes in solution. The molecular structures of 12a , b in the solid state are reported confirming the monomeric architecture with coordination number 4 at silver, which is setup by a chelate-bonded ( κ 2 -S,S′) S 2 CNR(C 2 H 4 OH) unit and two coordinated PPh 3 ligands. The thermal behavior of selected samples was studied by thermogravimetry. Depending on R, R′ and the number of phosphines n , decomposition occurs in varying temperature ranges giving different decomposition residues (Cu x S, x  = 1.96, 2; Ag, Ag 2 S), which were characterized by XRPD.