Experimental Electron Density in a Transition Metal Dimer:  Metal−Metal and Metal−Ligand Bonds

1998 ◽  
Vol 120 (51) ◽  
pp. 13429-13435 ◽  
Author(s):  
Piero Macchi ◽  
Davide M. Proserpio ◽  
Angelo Sironi
Keyword(s):  
Transition Metal ◽  
Electron Density ◽  
Metal Metal ◽  
Experimental Electron Density ◽  
Metal Ligand

scholarly journals Experimental and theoretical characterization of the Zn—Zn bond in [Zn2(η5-C5Me5)2]

2007 ◽  
Vol 63 (6) ◽  
pp. 862-868 ◽  
Author(s):  
Juan F. Van der Maelen ◽  
Enrique Gutiérrez-Puebla ◽  
Ángeles Monge ◽  
Santiago García-Granda ◽  
Irene Resa ◽  
...  
Keyword(s):  
Electron Density ◽  
Density Functional ◽  
Topological Analysis ◽  
Open Shell ◽  
Synchrotron Diffraction ◽  
Functional Theory ◽  
Metal Metal ◽  
Moller Plesset ◽  
Experimental Electron Density

The existence and characterization of a bond between the Zn atoms in the recently synthesized complex [Zn2(η5-C5Me5)2], as well as between Zn and ligand C atoms is firmly based on neutron diffraction and low-temperature X-ray synchrotron diffraction experiments. The multipolar analysis of the experimental electron density and its topological analysis by means of the `Atoms in Molecules' (AIM) approach reveals details of the Zn—Zn bond, such as its open-shell intermediate character (the results are consistent with a typical metal–metal single bond), as well as many other topological properties of the compound. Experimental results are also compared with theoretical ab initio calculations of the DFT (density functional theory) and MP2 (Møller-Plesset perturbation theory) electron densities, giving a coherent view of the bonding in the complex. For instance, charges calculated from the AIM approach applied to the atomic basin of each Zn atom are, on average, +0.72 e from both the experimental and the theoretical electron density, showing a moderate charge transfer from the metal, confirmed by the calculated topological indexes.

scholarly journals Metal–Metal and Metal–Ligand Bonding in Trinuclear Vinylidene Rhenium-Iron-Platinum Complex Studied by Topological Analysis of Electron Density

2020 ◽  
pp. 553-564
Author(s):  
Aleksey M. Shor ◽  
Svetlana S. Laletina ◽  
Anatoly I. Rubaylo ◽  
Elena A. Ivanova-Shor
Keyword(s):  
Electron Density ◽  
Density Functional ◽  
Topological Analysis ◽  
Density Functional Method ◽  
Platinum Complex ◽  
Functional Method ◽  
Iron Platinum ◽  
Metal Atoms ◽  
Metal Metal ◽  
Metal Ligand

Metal–metal and metal–ligand bonding in vinylidene ReFePt complex was studied by density functional method and topological analysis of electron density. Topological analysis did not found direct bonding between the metal atoms pointing to indirect metal–metal interaction mediated via the bridging vinylidene ligand. At the same time, the delocalization index δ(Fe,Pt) reveals the strong Fe–Pt interaction that allows for supposing a chemical bonding between these atoms

Dinuclear first-row transition metal–(C8Me6)2complexes: metal–metal and metal–ligand bonds determined by the d electron configuration of the metal atom

2016 ◽  
Vol 40 (3) ◽  
pp. 1988-1996 ◽  
Author(s):  
Xiuli Yan ◽  
Xiaoyan Li ◽  
Zheng Sun ◽  
Qingzhong Li ◽  
Lingpeng Meng
Keyword(s):  
Transition Metal ◽  
Metal Atom ◽  
Electron Configuration ◽  
Metal Metal ◽  
Metal Ligand

The nature and strength of the metal–metal and metal–ligand bonds depend on the d electron configuration of the transition metal.

Chemical bonding in groups 10, 11, and 12 transition metal homodimers — An electron density study

2013 ◽  
Vol 91 (7) ◽  
pp. 583-590 ◽  
Author(s):  
SeyedAbdolreza Sadjadi ◽  
Chérif F. Matta ◽  
I.P. Hamilton
Keyword(s):  
Transition Metal ◽  
Critical Point ◽  
Electron Density ◽  
Exponential Dependence ◽  
Bond Critical Point ◽  
Bond Dissociation Energies ◽  
Covalent Bonds ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Metal Metal

The properties of metal–metal bonding for transition metal homonuclear diatomics from groups 10, 11 and 12 are studied within the framework of the quantum theory of atoms in molecules (QTAIM) at the coupled cluster CCSD and CCSD(T) levels of theory. A novel approximate method developed by Keith and Frisch is used to augment electron densities calculated with pseudopotentials with the missing relativistic core densities to obtain approximations to the total densities of the dimers. The calculated delocalization indices for group 10 dimers are: Ni2 (1.6), Pd2 (0.44, an outlier in the group), and Pt2 (1.8); for group 11 dimers: Cu2 and Ag2 (1.01), and Au2 (1.13), all covalent bonds; for group 12: Zn2 (0.06), Cd2 (0.08), and Hg2 (0.09), all consistent with weak van der Waals complexes. The picture of bonding obtained by examining the values of the electron density at the bond critical points is consistent with the one obtained on the basis of these delocalization indices. A curious linear (instead of exponential) dependence of the delocalization index on the electron density at the bond critical point is presented here as an observation and will be investigated in more depth in later work. Several correlations between bond properties and bond dissociation energies are also explored. It is found that, with the exception of the Ni2 dimer that exhibits considerable multi-reference character, there are correlations between the calculated bond dissociation energies of the studied diatomics and several bond critical point properties. These correlations are novel as they span a set of bonds between different pairs of elements, while traditionally these correlations were reported for bonds between the same pair or elements but with different substituents.

ChemInform Abstract: Fragmentation of Realgar, As4S4, Controlled by Transition Metal-Ligand Systems.

ChemInform ◽  
1987 ◽  
Vol 18 (51) ◽  
Author(s):  
M. DI VAIRA ◽  
P. STOPPIONI ◽  
M. PERUZZINI
Keyword(s):  
Transition Metal ◽  
Metal Ligand

An experimental electron density study on “1-zirconacyclopent-3-yne”

2006 ◽  
pp. 1233 ◽  
Author(s):  
Daisuke Hashizume ◽  
Noriyuki Suzuki ◽  
Teiji Chihara
Keyword(s):  
Electron Density ◽  
Experimental Electron Density ◽  
Density Study

Symmetry Violations in Partially Oxidized One-Dimensional (1D)Transition Metal Polymers. Metal-Ligand-Metal(M-L-M) Bridged Systems

1984 ◽  
Vol 39 (9) ◽  
pp. 807-829
Author(s):  
Michael C. Böhm
Keyword(s):  
Transition Metal ◽  
Density Wave ◽  
Tight Binding ◽  
Mean Field ◽  
Valence Bond ◽  
Hole State ◽  
One Dimensional ◽  
Metal Derivatives ◽  
A Charge ◽  
Metal Ligand

The band structure of the metal-ligand-metal (M-L-M) bridged quasi one-dimensional (1D) cyclopentadienylmanganese polymer, MnCp 1, has been studied in the unoxidized state and in a partly oxidized modification with one electron removed from each second MnCp fragment. The tight-binding approach is based on a semiempirical self-consistent-field (SCF) Hartree-Fock (HF) crystal orbital (CO) model of the INDO-type (intermediate neglect of differential overlap) combined with a statistical averaging procedure which has its origin in the grand canonical ensemble. The latter approximation allows for an efficient investigation of violations of the translation symmetries in the oxidized 1D material. The oxidation process in 1 is both ligand- and metal-centered (Mn 3d-2 states). The mean-field minimum corresponds to a charge density wave (CDW) solution with inequivalent Mn sites within the employed repeat-units. The symmetry adapted solution with electronically identical 3d centers is a maximum in the variational space. The coupling of this electronic instability to geometrical deformations is also analyzed. The ligand amplitudes encountered in the hole-state wave function prevent extremely large charge separations between the 3d centers which are found in ID systems without bridging moieties (e.g. Ni(CN)2-5 chain). The symmetry reduction in oxidized 1 is compared with violations of spatial symmetries in finite transition metal derivatives and simple solids. The stabilization of the valence bond-type (VB) solution is physically rationalized (i.e. left-right correlations between the 3d centers). The computational results derived for 1 are generalized to oxidized transition metal chains with band occupancies that are simple fractions of the number of stacking units and to 1D systems that deviate from this relation. The entropy-influence for temperatures T ≠ 0 is shortly discussed (stabilization of domain or cluster structures).

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