Charge Density in Transition Metal Clusters:  Supported vs Unsupported Metal−Metal Interactions

Macchi, Piero; Garlaschelli, Luigi; Martinengo, Secondo; Sironi, Angelo

doi:10.1021/ja9918977

Cited by 120 publications

(98 citation statements)

References 15 publications

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“…This is similar to the QTAIM description of bridging carbonyl [11,30,31,56] and phosphane [55] ligands but clearly contradicts the experimental QTAIM results for 1, which provided two B À Mn bond VSCCs, each one of them pointing from the bridging boron atom towards one of the Mn centers. [9] While the experimental study is thus more consistent with a description of the bridging ligand as a substituted borane, the B3 LYP/ TZVP picture is that of a delocalized three-center bond of a genuine borylene.…”

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confidence: 38%

“…At all levels, the latter methylenebridged complex exhibits only one VSCC, consistent with the delocalized three-center bonding picture that is common also for bridging carbonyl ligands. [11,30,31,56] In contrast, with GGA functionals (BP86, BLYP), complexes 1 and 4 feature two VSCCs and thus a localized two-center bonding picture. Exact-exchange admixture changes this to a delocalized picture with one VSCC already at B3 LYP level (and also with 50 % exact exchange at BHLYP level).…”

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confidence: 99%

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Comparative Analysis of Electron‐Density and Electron‐Localization Function for Dinuclear Manganese Complexes with Bridging Boron‐ and Carbon‐Centered Ligands

Götz

Kaupp

Braunschweig

2008

Chemistry A European J

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Bonding in borylene-, carbene-, and vinylidene-bridged dinuclear manganese complexes [MnCp(CO)(2)](2)X (X = B-tBu, B = NMe(2), CH(2), C=CH(2)) has been compared by analyses based on quantum theory of atoms in molecules (QTAIM), on the electron-localization function (ELF), and by natural-population analyses. All of the density functional theory based analyses agree on the absence of a significant direct Mn-Mn bond in these complexes and confirm a dominance of delocalized bonding via the bridging ligand. Interestingly, however, the topology of both charge density and ELF related to the Mn-bridge-Mn bonding depend qualitatively on the chosen density functional (except for the methylene-bridged complex, which exhibits only one three-center-bonding attractor both in -nabla(2)rho and in ELF). While gradient-corrected functionals provide a picture with localized two-center X-Mn bonding, increasing exact-exchange admixture in hybrid functionals concentrates charge below the bridging atom and suggests a three-center bonding situation. For example, the bridging boron ligands may be described either as substituted boranes (e.g., at BLYP or BP86 levels) or as true bridging borylenes (e.g., at BHLYP level). This dependence on the theoretical level appears to derive from a bifurcation between two different bonding situations and is discussed in terms of charge transfer between X and Mn, and in the context of self-interaction errors exhibited by popular functionals.

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confidence: 38%

mentioning

confidence: 99%

Comparative Analysis of Electron‐Density and Electron‐Localization Function for Dinuclear Manganese Complexes with Bridging Boron‐ and Carbon‐Centered Ligands

Götz

Kaupp

Braunschweig

2008

Chemistry A European J

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“…67 In fact, the presence of MC bridge bond paths, inwardly curved in the M-C-M ring was recognized as a clear sign of multi-center bonding. Moreover, this view is in agreement with the DAFH picture, later proposed by Ponec et al 32,34 The analysis of the individual E 136 au), in which the electrostatic part is overwhelming.…”

Section: Theory and Computational Detailsmentioning

confidence: 99%

An Interacting Quantum Atoms Analysis of the Metal–Metal Bond in [M₂(CO)₈]ⁿ Systems

et al. 2015

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The metal-metal interaction in policarbonyl metal clusters remains one of the most challenging and controversial issues in metal-organic chemistry, being at heart of a generalized understanding of chemical bonding and of specific applications of these molecules. In this work, the interacting quantum atoms (IQA) approach is used to study the metal-metal interaction in dimetal polycarbonyl dimers, analysing bridgedclusters. In all systems, a delocalized covalent bond is found to occur, involving the metals and the carbonyls, but the global stability of the dimers mainly originates from the coulombic attraction between the metals and the oxygens.

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“…The failure of this criterion to characterize typical covalent molecules has also been reported. [31,32] Several other parameters, such as local kinetic energy density G(r c ), local potential energy density V(r c ), local electron energy density H(r c ), and ratios ÀG(r c )/V(r c ) and G(r c )/1 (r c ), were introduced to describe the nature of bonding. It has been reported in the literature that a bond can be considered to have partial covalent character if gN > 2 1(r c ) > 0 and H(r c ) < 0.…”

Section: Computational Detailsmentioning

confidence: 99%

Ab Initio Study on the Stability of Ng_nBe₂N₂, Ng_nBe₃N₂and NgBeSiN₂Clusters

et al. 2014

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The global minima of Be2N2, Be3N2 and BeSiN2 clusters are identified using a modified stochastic kick methodology. The structure, stability and bonding nature of these clusters bound to noble gas (Ng) atoms are studied at the MP2/def2-QZVPPD level of theory. Positive Be-Ng bond dissociation energy, which gradually increases down Group 18 from He to Rn, indicates the bound nature of Ng atoms. All of the Ng-binding processes are exothermic in nature. The Xe and Rn binding to Be2N2 and Be3N2 clusters and Ar-Rn binding to BeSiN2 are exergonic processes at room temperature; however, for the lighter Ng atoms, lower temperatures are needed. Natural population analysis, Wiberg bond index computations, electron density analysis, and energy decomposition analysis are performed to better understand the nature of Be-Ng bonds.

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Charge Density in Transition Metal Clusters: Supported vs Unsupported Metal−Metal Interactions

Cited by 120 publications

References 15 publications

Comparative Analysis of Electron‐Density and Electron‐Localization Function for Dinuclear Manganese Complexes with Bridging Boron‐ and Carbon‐Centered Ligands

Comparative Analysis of Electron‐Density and Electron‐Localization Function for Dinuclear Manganese Complexes with Bridging Boron‐ and Carbon‐Centered Ligands

An Interacting Quantum Atoms Analysis of the Metal–Metal Bond in [M₂(CO)₈]ⁿ Systems

Ab Initio Study on the Stability of Ng_nBe₂N₂, Ng_nBe₃N₂and NgBeSiN₂Clusters

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Charge Density in Transition Metal Clusters: Supported vs Unsupported Metal−Metal Interactions

Cited by 120 publications

References 15 publications

Comparative Analysis of Electron‐Density and Electron‐Localization Function for Dinuclear Manganese Complexes with Bridging Boron‐ and Carbon‐Centered Ligands

Comparative Analysis of Electron‐Density and Electron‐Localization Function for Dinuclear Manganese Complexes with Bridging Boron‐ and Carbon‐Centered Ligands

An Interacting Quantum Atoms Analysis of the Metal–Metal Bond in [M2(CO)8]n Systems

Ab Initio Study on the Stability of NgnBe2N2, NgnBe3N2and NgBeSiN2Clusters

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An Interacting Quantum Atoms Analysis of the Metal–Metal Bond in [M₂(CO)₈]ⁿ Systems

Ab Initio Study on the Stability of Ng_nBe₂N₂, Ng_nBe₃N₂and NgBeSiN₂Clusters