Donor‐acceptor interactions: Transition metal carbonyl group ligand [TM(CO)6]qcomplexes. A case study at correlated level from the topological density point of view

Bochicchio, Roberto C.; Lobayan, Rosana M.; Valle, Carlos Pérez del

doi:10.1002/qua.25876

Cited by 4 publications

(1 citation statement)

References 51 publications

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“…[4][5][6][7][8] This has led many chemists to study the bondingb etween Ma nd CO in metal-carbonyl complexes in more detail. [9][10][11][12][13] When carbonyl coordinates to at ransition metal, the CÀO bond length can either increase or decrease with respect to the bond length of isolated CO. In the case of bond length expansion, the carbonyl complex is said to be classical, which is usually explained by the Dewar-Chatt-Duncanson (DCD) model (Scheme1).…”

Section: Introductionmentioning

confidence: 99%

The Nature of Nonclassical Carbonyl Ligands Explained by Kohn–Sham Molecular Orbital Theory

Lubbe

Vermeeren

Guerra

et al. 2020

Chemistry A European J

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When carbonyl ligands coordinate to transition metals, their bond distance either increases (classical) or decreases (nonclassical) with respect to the bond length in the isolated CO molecule. C−O expansion can easily be understood by π‐back‐donation, which results in a population of the CO's π*‐antibonding orbital and hence a weakening of its bond. Nonclassical carbonyl ligands are less straightforward to explain, and their nature is still subject of an ongoing debate. In this work, we studied five isoelectronic octahedral complexes, namely Fe(CO)62+, Mn(CO)6+, Cr(CO)6, V(CO)6− and Ti(CO)62−, at the ZORA‐BLYP/TZ2P level of theory to explain this nonclassical behavior in the framework of Kohn–Sham molecular orbital theory. We show that there are two competing forces that affect the C−O bond length, namely electrostatic interactions (favoring C−O contraction) and π‐back‐donation (favoring C−O expansion). It is a balance between those two terms that determines whether the carbonyl is classical or nonclassical. By further decomposing the electrostatic interaction ΔVelstat into four fundamental terms, we are able to rationalize why ΔVelstat gives rise to the nonclassical behavior, leading to new insights into the driving forces behind C−O contraction.

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Section: Introductionmentioning

confidence: 99%

The Nature of Nonclassical Carbonyl Ligands Explained by Kohn–Sham Molecular Orbital Theory

Lubbe

Vermeeren

Guerra

et al. 2020

Chemistry A European J

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Substituent Effect Parameters: Extending the Applications to Organometallic Chemistry

Remya

Suresh

2020

ChemPhysChem

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Typically, metal complexes are constituted of an acceptor metal ion and one or more Iigands containing the donor atoms. Accordingly, the properties of a metal complex are equally dependent on the nature of the metal ion and the ligands. Minute structural variations in the ligand will may result in linear changes in the respective energetic parameters and such linear relationships have paramount importance in organometallic chemistry. The variation in ligands is virtually limitless and substantial because of the extent of organic chemistry available for the modelling of desirable ligands, apart from the variation in metal ions. Anyhow, there is still a need for new parameters for the design and quantification of new ligands which in turn leads to the synthesis of metal complexes with possibly predictable chemical properties. Previous studies have demonstrated that quantum chemically derived molecular electrostatic potential (MESP) parameters can be listed as one of the superior quantifiers in this regard, which can act as an effective ligand electronic parameter. The interaction between the ligand part and metal-containing part will be crucial in assessing the reactivity of organometallic complexes. Here we are applying MESP based substituent constants derived from substituted benzenes to forecast the interaction energies in (pyr*)W(CO) 5 , (NHC*)Mo(CO) 5 and (η 6 -arene*)Cr(CO) 3 complexes. Ligands and metal ions are varied in each case for better understanding and transparency.[a] G.

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Group VI Metal Complexes of Carbon Monoxide and Isocyanides

Fischer

2022

Comprehensive Organometallic Chemistry IV

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Donor‐acceptor interactions: Transition metal carbonyl group ligand [TM(CO)₆]^qcomplexes. A case study at correlated level from the topological density point of view

Cited by 4 publications

References 51 publications

The Nature of Nonclassical Carbonyl Ligands Explained by Kohn–Sham Molecular Orbital Theory

The Nature of Nonclassical Carbonyl Ligands Explained by Kohn–Sham Molecular Orbital Theory

Substituent Effect Parameters: Extending the Applications to Organometallic Chemistry

Group VI Metal Complexes of Carbon Monoxide and Isocyanides

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