Theoretical studies on structures and reactivities of organocuprate(I) and organocopper(III) species

Systematic evaluation of method and basis set on the structure and energetics of organocuprate(I) and organocopper(III) species has been carried out. Various structures of organocuprate(I) and organocuprate(III) complexes were optimized with the HF, MP2, and B3LYP methods, and compared with the structures determined by X‐ray crystallography (i.e., Me2Cu(I)−, (CF3)4Cu(III)−). Both the MP2 and B3LYP methods reasonably reproduce the X‐ray structures while the HF method does not. Using larger basis set and incorporating the relativistic effects for Cu afford the best results. In the studies on the energetics of a LiCu cluster model (Me2CuLi · LiCl) and Me3Cu model with the MP2, MP3, MP4DQ, MP4SDQ, CCSD(T), and B3LYP methods, the B3LYP method gives energetics similar to those obtained with the CCSD(T) method with much less cost, and hence, is judged to be the best practical method. The studies have shown that B3LYP method with the basis set incorporating the relativistic effective core potentials for Cu and the 6‐31G* basis set for the rest is the theoretical method that is the most cost‐effective for the studies of the structure and energetics of organocuprate(I) and organocopper(III) species. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1401–1409, 2003