TY - JOUR

T1 - Quantum-chemical study of donor-acceptor interactions in chelate dicarbonyl complexes of rhodium(I)

AU - Sizova, Olga V.

AU - Sokolov, A. Yu

AU - Skripnikov, L. V.

PY - 2007/11

Y1 - 2007/11

N2 - DFT calculations were used to analyze the electronic structures of 15 mono- and dicarbonyl rhodium(I) complexes with bidentate O,O-, N,N-, and N,O-donor ligands. The characteristics describing the metal-CO bond (bond length and spin-spin coupling constant J(CRh)) were found to depend on which of the donor atoms (N or O) is trans to the carbonyl group. Because of this, the trans-effect transmitted along the σ-bonds can be judged from the values of these characteristics. The characteristics whose values are determined by the populations of the π-antibonding orbitals of the CO groups primarily depend on the cis-partners in the coordination sphere.

AB - DFT calculations were used to analyze the electronic structures of 15 mono- and dicarbonyl rhodium(I) complexes with bidentate O,O-, N,N-, and N,O-donor ligands. The characteristics describing the metal-CO bond (bond length and spin-spin coupling constant J(CRh)) were found to depend on which of the donor atoms (N or O) is trans to the carbonyl group. Because of this, the trans-effect transmitted along the σ-bonds can be judged from the values of these characteristics. The characteristics whose values are determined by the populations of the π-antibonding orbitals of the CO groups primarily depend on the cis-partners in the coordination sphere.

UR - http://www.scopus.com/inward/record.url?scp=36348929976&partnerID=8YFLogxK

U2 - 10.1134/S1070328407110036

DO - 10.1134/S1070328407110036

M3 - Article

AN - SCOPUS:36348929976

VL - 33

SP - 800

EP - 808

JO - Russian Journal of Coordination Chemistry

JF - Russian Journal of Coordination Chemistry

SN - 1070-3284

IS - 11

ER -