Copper Diamidocarbene Complexes: Characterization of Monomeric to Tetrameric Species

Treatment of CuCl with 1 equiv of
the in situ prepared N-mesityl-substituted diamidocarbene
6-MesDAC produced a mixture of the dimeric and trimeric copper complexes
[(6-MesDAC)­CuCl]2 (1) and [(6-MesDAC)2(CuCl)3] (2). Combining CuCl with
isolated, free 6-MesDAC in 1:1 and 3:2 ratios gave just 1 and 2, respectively, while increasing the ratio to
>5:1 allowed the isolation of small amounts of the tetrameric copper
complex [(6-MesDAC)2(CuCl)4] (3). Efforts to bring about metathesis reactions of 1 with
MOtBu (M = Li, Na, K) proved successful only for M = Li
to afford the spectroscopically characterized ate product [(6-MesDAC)­CuCl·LiOtBu·2THF] (5). Attempts to crystallize this
species instead gave a 1:1 mixture of 1 and the monomer
[(6-MesDAC)­CuCl] (6). The X-ray structures of 1–3 and 1 + 6, along
with the cation [Cu­(6-MesDAC)2]+ (4), have been determined.