Quantum chemistry of organocuprates as intermediates of catalytic and photochemical reactions
| Autor: | Oleg I. Gromov, Elena N. Golubeva, Georgy M. Zhidomirov, Ekaterina M. Zubanova |
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| Rok vydání: | 2015 |
| Předmět: |
010405 organic chemistry
Chemistry Radical Electronic structure 010402 general chemistry Condensed Matter Physics Photochemistry 01 natural sciences Quantum chemistry Atomic and Molecular Physics and Optics 0104 chemical sciences Adduct Catalysis Computational chemistry Density functional theory Molecular orbital Physical and Theoretical Chemistry Group 2 organometallic chemistry |
| Zdroj: | International Journal of Quantum Chemistry. 116:295-300 |
| ISSN: | 0020-7608 |
| Popis: | 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 σ-bond CuC(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. © 2015 Wiley Periodicals, Inc. |
| Databáze: | OpenAIRE |
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