Quantum Chemistry of Organocuprates as Intermediates of Catalytic and Photochemical Reactions
International Journal of Quantum Chemistry
, E-ISSN: 1097-461X
||DFT, electronic structure, geometry, organocuprates, spectroscopy
Golubeva Elena N.
Gromov Oleg I.
Zhidomirov Georgy M.
Zubanova Ekaterina M.
Lomonosov Moscow State University, Lenin Hills 1-3, 119899, Russian Federation
N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 119991 Kosygina street, 4, Moscow, Russian Federation
Boreskov Institute of Catalysis (BIC), SO RAN, Prospekt Lavrentjeva, 5, Novosibirsk 630090, Russian Federation
Organocuprates (II) and (III) are intermediates of catalytic and photochemical reactions; nevertheless, in many cases their structure and reaction ability are unclear. Quantum-chemical calculations performed within the framework of density functional theory allowed to confirm some experimental evidences of existence of such organometallic compounds. In this article, composition and geometry of organocopper transients were estimated via comparing of experimental and calculated energies of electronic transitions and g-tensors. The formation of r-bond CuAC(sp3) in adducts of Cu(I) and Cu(II) complexes with alkyl-type radicals was corroborated by Natural Bonding Orbital analysis. The nuclearity of Cu(II) chloride complexes influences the mechanism of their interaction with alkyl radicals.