Synthesis, Spectroscopy, and Structures of Mono‐ and Dinuclear Copper(I) Halide Complexes with 1,3‐Imidazolidine‐2‐thiones

Copper(I) halides with triphenyl phosphine and imidaozlidine‐2‐thiones ( L ‐NMe, L ‐NEt, and L ‐NPh) in acetonitrile/methanol (or dichloromethane) yielded copper(I) mixed‐ligand complexes: mononuclear, namely, [CuCl(κ 1 ‐S‐ L ‐NMe)(PPh 3 ) 2 ] ( 1 ), [CuBr(κ 1 ‐S‐ L ‐NMe)(PPh 3 ) 2 ] ( 2 ), [CuBr(κ 1 ‐S‐ L ‐NEt)(PPh 3 ) 2 ] ( 5 ), [CuI(κ 1 ‐S‐ L ‐NEt)(PPh 3 ) 2 ] ( 6 ), [CuCl(κ 1 ‐S‐ L ‐NPh)(PPh 3 ) 2 ] ( 7 ), and [CuBr(κ 1 ‐S‐ L ‐NPh)(PPh 3 ) 2 ] ( 8 ), and dinuclear, [Cu 2 (κ 1 ‐I) 2 (μ‐S‐ L ‐NMe) 2 (PPh 3 ) 2 ] ( 3 ) and [Cu 2 (μ‐Cl) 2 (κ 1 ‐S‐ L ‐NEt) 2 (PPh 3 ) 2 ] ( 4 ). All complexes were characterized with analytical data, IR and NMR spectroscopy, and X‐ray crystallography. Complexes 2 – 4 , 7 , and 8 each formed crystals in the triclinic system with P $\bar{1}$ space group, whereas complexes 1 , 5 , and 6 crystallized in the monoclinic crystal system with space groups P 2 1 / c , C 2/ c , and P 2 1 / n , respectively. Complex 2 has shown two independent molecules, [(CuBr(κ 1 ‐S‐ L ‐NMe)(PPh 3 ) 2 ] and [CuBr(PPh 3 ) 2 ] in the unit cell. For X = Cl, the thio‐ligand bonded to metal as terminal in complex 4 , whereas for X = I it is sulfur‐bridged in complex 3 .