Characterization of metal – metal and metal – ligand interactions in binuclear MnPt vinylidene complexes by molecular orbital and charge density analyses

Описание

Тип публикации: статья из журнала

Год издания: 2022

Идентификатор DOI: 10.1016/j.jorganchem.2021.122249

Ключевые слова: binuclear vinylidene complexes, charge decomposition analysis, metal – ligand interaction, metal – metal interaction, natural population analysis, topological analysis

Аннотация: Density functional theory and the extended charge decomposition analysis (ECDA), the natural population analysis (NPA) as well as the quantum theory of atoms in molecules (QTAIM) were used to gain insight into the nature of metal–metal and metal–ligand interactions in binuclear manganese–platinum vinylidene complexes with phosphineПоказать полностьюligands at the Pt atom: Cp(CO)2MnPt(μ-C=CHPh)(P-P) (1 P-P=(PPh3)2, 2 P-P=dppm). The complexes 1 and 2 can be represented as π-complexes of the Pt-phosphine moiety (M) with the metalla-allene ligand Cp(CO)2Mn=C=CHPh (L). The substitution of PPh3 groups at the Pt atom by dppm ligand leads to a growth of the L ← M back-interaction as the result of approaching the CO group at the Mn atom to the Pt atom induced by the decrease in steric disincentives caused by phosphine ligands. Topological analysis of the charge density points to the indirect metal – metal bonding mediated by a couple of the 2e-2c metal –carbon interactions and the semi-bridging coordinated carbonyl group. © 2022 Elsevier B.V.

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Издание

Журнал: Journal of Organometallic Chemistry

Выпуск журнала: Vol. 961

Номера страниц: 122249

ISSN журнала: 0022328X

Издатель: Elsevier B.V.

Персоны

  • Shor A.M. (Institute of Chemistry and Chemical Technology SB RAS, Federal Research Center “Krasnoyarsk Scientific Center SB RAS”, Akademgorodok, 50-24, Krasnoyarsk, 660036, Russian Federation)
  • Nasluzov V.A. (Institute of Chemistry and Chemical Technology SB RAS, Federal Research Center “Krasnoyarsk Scientific Center SB RAS”, Akademgorodok, 50-24, Krasnoyarsk, 660036, Russian Federation)
  • Rubaylo A.I. (Institute of Chemistry and Chemical Technology SB RAS, Federal Research Center “Krasnoyarsk Scientific Center SB RAS”, Akademgorodok, 50-24, Krasnoyarsk, 660036, Russian Federation, Siberian Federal University, Svobodny Prospect 79, Krasnoyarsk, 660041, Russian Federation)
  • Ivanova-Shor E.A. (Institute of Chemistry and Chemical Technology SB RAS, Federal Research Center “Krasnoyarsk Scientific Center SB RAS”, Akademgorodok, 50-24, Krasnoyarsk, 660036, Russian Federation)