Metal–Metal and Metal–Ligand Bonds in (η5-C5H5)2M2 (M = Be, Mg, Ca, Ni, Cu, Zn)

Li, Xiaoyan; Huo, Suhong; Zeng, Yanli; Sun, ZhengMing; Zheng, Shourong; Meng, Lingpeng

doi:10.1021/om301110j

Cited by 46 publications

(34 citation statements)

References 47 publications

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“…It also gives insight into the origins of the relative bond strengths in metal-metal bonds: although both Mg-Mg and Zn-Zn bonds have strong covalent stabilization, the more easily oxidized Zn is further stabilized by ionic resonances, making it a much stronger bond. This was hinted at in a recent QTAIM study, which showed that main group-main group bonds in M2Cp 2 had more "covalent characteristics", while transition metal-transition metal bonds had "closed shell ionic characteristics" (60).…”

Section: Resultsmentioning

confidence: 90%

Energy decomposition analysis of single bonds within Kohn–Sham density functional theory

Levine

Head‐Gordon

2017

Proc. Natl. Acad. Sci. U.S.A.

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An energy decomposition analysis (EDA) for single chemical bonds is presented within the framework of Kohn-Sham density functional theory based on spin projection equations that are exact within wave function theory. Chemical bond energies can then be understood in terms of stabilization caused by spin-coupling augmented by dispersion, polarization, and charge transfer in competition with destabilizing Pauli repulsions. The EDA reveals distinguishing features of chemical bonds ranging across nonpolar, polar, ionic, and charge-shift bonds. The effect of electron correlation is assessed by comparison with Hartree-Fock results. Substituent effects are illustrated by comparing the C-C bond in ethane against that in bis(diamantane), and dispersion stabilization in the latter is quantified. Finally, three metal-metal bonds in experimentally characterized compounds are examined: a [Formula: see text]-[Formula: see text] dimer, the [Formula: see text]-[Formula: see text] bond in dizincocene, and the Mn-Mn bond in dimanganese decacarbonyl.

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Section: Resultsmentioning

confidence: 90%

Energy decomposition analysis of single bonds within Kohn–Sham density functional theory

Levine

Head‐Gordon

2017

Proc. Natl. Acad. Sci. U.S.A.

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“…Generally speaking, the electron density at the BCP reliably reflects the strength of a bond. 94 The numerical values of the ELF for all the considered molecules are listed in Table 1. A negative electron density Laplacian shows the excess potential energy at BCP introducing electronic charge concentration in the inter-nuclear region and implies a shared interaction as in covalent bonds.…”

Section: Resultsmentioning

confidence: 99%

First principles optimally tuned range-separated density functional theory for prediction of phosphorus–hydrogen spin–spin coupling constants

Alipour

Fallahzadeh

2016

Phys. Chem. Chem. Phys.

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Optimally tuned range-separated (OT-RS) density functional theory (DFT) is a recent endeavor toward the systematic and non-empirical routes for designing the exchange-correlation functionals. Herein, a detailed analysis of the development and benchmarking of the OT-RS functionals for predicting the experimental nuclear magnetic resonance (NMR) spin-spin coupling constants (SSCCs) in diverse sets of compounds containing phosphorus-hydrogen (P-H) bonds has been done. More specifically, besides analyzing the performances of standard long-range corrected (LC) functionals, two new non-empirical OT-RS functionals are proposed for this purpose. Furthermore, we dissect the importance of both short- and long-range exchange contributions and range separation parameters in LC density functional calculations of P-H SSCCs. It is shown that the proposed functionals not only give an improved description of SSCCs with respect to conventional LC approximations but also in many cases perform better than other functionals from various rungs. The accountability of the new models for predicting the SSCCs and their components in continuum solvents has also been examined and validated. Overall, we hope that this contribution stimulates the development of novel OT-RS DFT approximations based on theoretical arguments as a methodology with both high accuracy and computational efficiency for modeling the NMR parameters.

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“…Recently, AIM theory and ELF methods have been shown to be powerful methods to explore chemical bonding [71][72][73][74] . AIM theory uses novel descriptors, such as the electron-density distributions at the bond critical point (BCP), to provide deep insight into the 25 nature of the chemical bond.…”

Section: Topological Analysis Of Electron Densitymentioning

confidence: 99%

“…And the occurrence of NNA depends on calculated basis set and 55 method [60,84,85] ,or depends on a suitable match of radial shell and internuclear separation [71,86] .The NNA are tested by using HF, B3LYP, and M062X methods with 6-311G(d), 6-311+G(d), and 6-311G(2df), and 6-311+G(2df) basis sets. The calculated shows that the NNA are exist at all the above calculated levels.…”

Section: Aim Analysismentioning

confidence: 99%

Influences of the substituents on the M–M bonding in Cp₄Al₄ and Cp₂M₂X₂ (M = B, Al, Ga; Cp = C₅H₅, X = halogen)

Sun

et al. 2015

Dalton Trans.

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Although the geometries of CpAl4 (Cp* = C5Me5) and Cp4Al4 (Cp = C5H5) are similar, CpAl4 is more stable than Cp4Al4. CpAl2I2 is the first complex involving an Al(ii)-Al(ii) bond to be supported by Cp-type ligands. In this work, the stability of CpAl4 and Cp4Al4 (Cp = C5H5), the nature of M-M bonding in Cp2M2X2 (M = B, Al, and Ga), and the influences of the X atom on the M-M bonds have been analyzed and compared within the framework of the atoms in molecules (AIM) theory, electron localization function (ELF), energy decomposition analysis (EDA), and natural bond orbital (NBO) analysis. The calculated results show that CpAl4 is more stable than Cp4Al4 because of HH interactions between the methyl groups on the same and different Cp rings and not because of the Al-Al bonds. In Cp2M2X2, the B-B bond is stronger than the Al-Al and Ga-Ga bonds. The B-B bond is most consistent with covalent bonding, whereas the Al-Al and Ga-Ga bonds are more consistent with metallic bonding. The strengths of the B-B bond increase in the sequence X = F, Cl, Br, and I, whereas the Al-Al and Ga-Ga bonds decrease in the sequence X = F, Cl, Br, and I. The different change tendencies arise from the different M-M bonds and the orbital interactions between atoms X and M.

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Metal–Metal and Metal–Ligand Bonds in (η⁵-C₅H₅)₂M₂ (M = Be, Mg, Ca, Ni, Cu, Zn)

Cited by 46 publications

References 47 publications

Energy decomposition analysis of single bonds within Kohn–Sham density functional theory

Energy decomposition analysis of single bonds within Kohn–Sham density functional theory

First principles optimally tuned range-separated density functional theory for prediction of phosphorus–hydrogen spin–spin coupling constants

Influences of the substituents on the M–M bonding in Cp₄Al₄ and Cp₂M₂X₂ (M = B, Al, Ga; Cp = C₅H₅, X = halogen)

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Metal–Metal and Metal–Ligand Bonds in (η5-C5H5)2M2 (M = Be, Mg, Ca, Ni, Cu, Zn)

Cited by 46 publications

References 47 publications

Energy decomposition analysis of single bonds within Kohn–Sham density functional theory

Energy decomposition analysis of single bonds within Kohn–Sham density functional theory

First principles optimally tuned range-separated density functional theory for prediction of phosphorus–hydrogen spin–spin coupling constants

Influences of the substituents on the M–M bonding in Cp4Al4 and Cp2M2X2 (M = B, Al, Ga; Cp = C5H5, X = halogen)

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Metal–Metal and Metal–Ligand Bonds in (η⁵-C₅H₅)₂M₂ (M = Be, Mg, Ca, Ni, Cu, Zn)

Influences of the substituents on the M–M bonding in Cp₄Al₄ and Cp₂M₂X₂ (M = B, Al, Ga; Cp = C₅H₅, X = halogen)