Syntheses, solution behavior, and computational bond length analyses of trifluoromethyl and perfluoroethyl cuprate salts

Abstract Heteroleptic cuprate salts of the form [X-Cu-Y][(SIMes)2Cu] (SIMes = 1,3-dimesitylimidazolin-2-ylidene, X and Y = permutations of Cl, CF3, C2F5) were generated by equilibrating mixtures of [(SIMes)Cu-X] and [(SIMes)Cu-Y] in CD2Cl2 solvent. The solubility features of the cuprates relative to the neutral species permitted the structural characterizations of new cuprates, including the first example of a mixed fluoroalkylated cuprate [(CF3)Cu(C2F5)][(SIMes)2Cu]. Computational studies (DFT and CCSD(T)) of fluoroalkylated cuprates generate Cu-C distances that are shorter than those in hydrocarbon analogues – a trend that in some cases may conflict with crystallographically determined values.