Author, as appears in the article.: Spivak M, López X, de Graaf C
Department: Química Física i Inorgànica
URV's Author/s: De Graaf, Cornelis / López Fernández, Javier
Keywords: Transition-metal Quintuple bond Quadruple bond Perturbation-theory Order Ligand Electronic-structure Chromium dimer Chemistry Ab-initio
Abstract: Extended metal atom chains constitute an interesting class of molecules from both theoretical and applied points of view. In the chromium-based series Cr2M(dpa)4X2 (with M = Zn, Ni, Fe, Mn, Cr), the direct metal-metal interactions span a wide range of possibilities and so do their associated properties. The multiplicity and symmetry components of the metal-metal bond are herein analyzed via the effective bond order (EBO) concept using complete active space self-consistent field wave functions and compared with similar bimetallic Cr2L4X2 systems. The bond multiplicity follows a trend dominated by the Cr-Cr distance which, in turn, depends on the nature of the axial ligand (X). Cr2M compounds present asymmetric structures with virtually no interaction between the Cr2 unit and M, whereas fully symmetric structures with delocalized bonding among the three metals are also possible in Cr3 complexes. In such cases, a strategy that involves localization of the molecular orbitals into each Cr-Cr pair is applied to quantify the contribution of each pair to the overall metal-metal bond multiplicity.
Thematic Areas: Química Physics, atomic, molecular & chemical Physical and theoretical chemistry Odontología Medicine (miscellaneous) Medicina ii Medicina i Materiais Interdisciplinar Geociências General medicine Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Chemistry, physical Biotecnología Biodiversidade Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 15205215
Author's mail: coen.degraaf@urv.cat javier.lopez@urv.cat
Author identifier: 0000-0001-8114-6658 0000-0003-0322-6796
Record's date: 2023-02-22
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: https://pubs.acs.org/doi/10.1021/acs.jpca.8b10124
Papper original source: Journal Of Physical Chemistry a. 123 (8): 1538-1547
APA: Spivak M, López X, de Graaf C (2019). Trends in the Bond Multiplicity of Cr2, Cr3, and Cr2M (M = Zn, Ni, Fe, Mn) Complexes Extracted from Multiconfigurational Wave Functions. Journal Of Physical Chemistry a, 123(8), 1538-1547. DOI: 10.1021/acs.jpca.8b10124
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Article's DOI: 10.1021/acs.jpca.8b10124
Entity: Universitat Rovira i Virgili
Journal publication year: 2019
Publication Type: Journal Publications
Repositori URV