Treatment of CuCl with 1 equiv of the in situ prepared N-mesitylsubstituted 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 (MOBu)-Bu-t (M = Li, Na, K) proved successful only for M = Li to afford the spectroscopically characterized ate product [(6-MesDAC)CuCl center dot(LiOBu)-Bu-t center dot 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.