Synthesis and Characterization of Copper Complexes with the N‐(2,6‐Diisopropylphenyl)‐N′‐acylthiourea Ligands

Abstract

Three N‐(2,6‐diisopropylphenyl)‐N′‐acylthiourea ligands [Ar′NHC(S)NHC(O)Ar; Ar′ = 2,6‐iPr2C6H3; Ar = p‐tBuC6H4 (1, L1), Mes (2, L2), and 1‐Naph (3, L3)] were synthesized and compared with the homologous ligand L0 (Ar = Ph) in terms of their resultant complexes with copper halides. The reaction of L1 with CuCl2 led to the formation of mononuclear L12CuCl (4), while treatment of L1 with CuX (X = Cl, Br) resulted in the adamantane cage complexes (L1CuX)4 (X = Cl, 5; Br, 6). These findings are similar to the results shown by its parent ligand L0. The reaction of L1 with CuI yielded the iodide‐bridged dimeric complex [L12Cu(µ‐I)]2 (7), in contrast to the ligand‐bridged dimer supported by L0. L2 readily afforded the mononuclear CuI complexes 8–10 coordinated by two or three ligands. L3 gave monomeric L33CuX (X = Cl, 11; Br, 12) and the iodide‐bridged dimeric [L32Cu(µ‐I)]2 (13). L3 can bind with CuI halides in a ratio of 1:1 to give complexes L3CuX(PPh3)2 (14–16), when Cu2X2(PPh3)3 (X = Cl, Br) or CuI(PPh3)3 were used as precursors. Treatment of (L1CuCl)4 (5), L22CuBr (8), and L33CuCl (11), respectively, with hot EtOH resulted in the formation of trans‐CuLn′2 (17–19) compounds. All compounds were characterized by single‐crystal X‐ray diffraction studies.