Orbital Splitting and Pairing Energy in Open-Shell Organometallics: A Study of Two Families of 16-Electron Complexes [Cp2M] (M = Cr, Mo, W) and [CpM(PH3)] (M = Co, Rh, Ir) - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue European Journal of Inorganic Chemistry Année : 2005

Orbital Splitting and Pairing Energy in Open-Shell Organometallics: A Study of Two Families of 16-Electron Complexes [Cp2M] (M = Cr, Mo, W) and [CpM(PH3)] (M = Co, Rh, Ir)

Résumé

The singlet–triplet gap for two families of 16-electron organometallic complexes has been examined in detail by DFT calculations at the B3LYP level with polarized basis sets on both metal and ligands. For the first family, the group 6 metallocenes (Cp2M with Cp = η5-C5H5 and M = Cr, Mo, W), the singlet–triplet gap (ES – ET) is always positive and decreases continuously on going from Cr to Mo to W. For the family of group 9 CpM(PH3), on the other hand, there is a decrease on going from Co to Rh, followed by a slight increase on going further to Ir. These trends have been analyzed in qualitative monoelectronic terms as a function of the competition between the pairing energy and the orbital gap. While the pairing energy decreases as expected in the order 3d >> 4d > 5d, the orbital gap varies in a different way for the two families and, though quantitatively less important, is responsible for the different trends. It is argued that changes in orbital gap are system-dependent for open-shell organometallic systems, thus it is not possible to establish a universal trend of singlet–triplet gaps for a homologous series of complexes with a group of transition metals.
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hal-03277934 , version 1 (06-07-2021)

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Rinaldo Poli, Ivo Cacelli. Orbital Splitting and Pairing Energy in Open-Shell Organometallics: A Study of Two Families of 16-Electron Complexes [Cp2M] (M = Cr, Mo, W) and [CpM(PH3)] (M = Co, Rh, Ir). European Journal of Inorganic Chemistry, 2005, 2005 (12), pp.2324-2331. ⟨10.1002/ejic.200400839⟩. ⟨hal-03277934⟩
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