TY - JOUR
T1 - A Multiconfigurational Theoretical Study of the Octamethyldimetalates of Cr(II), Mo(II), and Re(III): Revisiting the Correlation Between M-M Bond Length and the delta-delta* Transition Energy
AU - Ferrante, Francesco
AU - Sattelberger, Alfred P.
AU - Bursten, Bruce E.
AU - Gagliardi, Laura
PY - 2005
Y1 - 2005
N2 - Four compounds containing metal-metal quadruple bonds, the [M 2(CH3)8]n- ions (M = Cr, Mo, W, Re and n = 4, 4, 4, 2, respectively), have been studied theoretically using multiconfigurational quantum-chemical methods. The molecular structure of the ground state of these compounds has been determined and the energy of the δ → δ* transition has been calculated and compared with previous experimental measurements. The high negative charges on the Cr, Mo, and W complexes lead to difficulties in the successful modeling of the ground-state structures, a problem that has been addressed by the explicit inclusion of four Li+ ions in these calculations. The ground-state geometries of the complexes and the δ → δ* transition have been modeled with either excellent agreement with experiment (Re) or satisfactory agreement (Cr, Mo, and W).
AB - Four compounds containing metal-metal quadruple bonds, the [M 2(CH3)8]n- ions (M = Cr, Mo, W, Re and n = 4, 4, 4, 2, respectively), have been studied theoretically using multiconfigurational quantum-chemical methods. The molecular structure of the ground state of these compounds has been determined and the energy of the δ → δ* transition has been calculated and compared with previous experimental measurements. The high negative charges on the Cr, Mo, and W complexes lead to difficulties in the successful modeling of the ground-state structures, a problem that has been addressed by the explicit inclusion of four Li+ ions in these calculations. The ground-state geometries of the complexes and the δ → δ* transition have been modeled with either excellent agreement with experiment (Re) or satisfactory agreement (Cr, Mo, and W).
UR - http://hdl.handle.net/10447/34462
UR - https://pubs.acs.org/doi/abs/10.1021/ic050406i
M3 - Article
VL - 44
SP - 8476
EP - 8480
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
ER -