Simulating the effect of a triple bond to achieve the shortest main group metal–metal distance in diberyllium complexes: a computational study

2018 ◽  
Vol 47 (41) ◽  
pp. 14462-14467 ◽  
Author(s):  
Xue-Feng Zhao ◽  
Caixia Yuan ◽  
Si-Dian Li ◽  
Yan-Bo Wu ◽  
Xiaotai Wang
Keyword(s):  
Triple Bond ◽  
Computational Study ◽  
Main Group ◽  
Energy Minimum ◽  
Global Energy ◽  
Group Metal ◽  
Global Energy Minimum ◽  
Main Group Metal ◽  
Metal Metal

[Ne → Be2H3 ← Ne]+ represents the first global energy minimum having a main group metal–metal distance under 1.700 Å.

Main-group metal complexes of α-diimine ligands: structure, bonding and reactivity

2021 ◽  
Author(s):  
Rong Zhang ◽  
Yanchao Wang ◽  
Yanxia Zhao ◽  
Carl Redshaw ◽  
Igor L. Fedushkin ◽  
...  
Keyword(s):  
Metal Complexes ◽  
Small Molecule ◽  
Main Group ◽  
Group Metal ◽  
Diimine Ligands ◽  
Main Group Metal ◽  
Metal Metal ◽  
Low Valent

The use of dad (and bian) ligands in the stabilization of main-group complexes, in particular metal–metal-bonded compounds, as well as the small molecule reactivity of these (low-valent) metal complexes, is summarized.

N,N′-Dipp-o-phenylene-diamido Dianion: A Versatile Ligand for Main Group Metal–Metal-Bonded Compounds

2020 ◽  
Vol 39 (8) ◽  
pp. 1440-1447 ◽  
Author(s):  
Meimei Ma ◽  
Lingyi Shen ◽  
Huanhuan Wang ◽  
Yanxia Zhao ◽  
Biao Wu ◽  
...  
Keyword(s):  
Main Group ◽  
Group Metal ◽  
Main Group Metal ◽  
Metal Metal

Anti-Electrostatic Main Group Metal–Metal Bonds That Activate CO2

2021 ◽  
pp. 7545-7552
Author(s):  
Chuan-Kai Tang ◽  
Ya-Zhou Li ◽  
Fang Ma ◽  
Zexing Cao ◽  
Yirong Mo
Keyword(s):  
Main Group ◽  
Group Metal ◽  
Main Group Metal ◽  
Metal Metal ◽  
Metal Metal Bonds ◽  
Metal Bonds

Cyclopentadienyl complexes with transition metal – main group metal bonds. VII. 207Pb and 95Mo nuclear magnetic resonance studies on molybdenum and tungsten complexes [(η5-C5H5)(CO)3M]nPbR4−n (n = 1, R = Me, Et, Ph; n = 2, R = Ph)

1987 ◽  
Vol 65 (6) ◽  
pp. 1292-1297 ◽  
Author(s):  
Marek M. Kubicki ◽  
Jean-Yves Le Gall ◽  
René Kergoat ◽  
Luiz C. Gomes De Lima
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shifts ◽  
Main Group ◽  
Metal Interactions ◽  
Group Metal ◽  
Main Group Metal ◽  
Metal Metal ◽  
Diamagnetic Contribution ◽  
Nuclear Magnetic

Nuclear magnetic resonance measurements of metallic nuclei (δ 207Pb, δ 95Mo, and 1J(W–Pb)) have been carried out on dimetallic Cp(CO)3MPbR3 (M = Mo, W; R = Me, Et, Ph) and trimetallic [Cp(CO)3M]2PbPh2 (M = Mo, W) complexes. 207Pb chemical shifts increase in the sequence PbEt3 < PbMe3 < PbPh3 and are observed at higher fields in the tungsten compounds than in the molybdenum ones. It is suggested that both paramagnetic and diamagnetic contributions determine the overall shielding of lead, and that the higher field resonances of 207Pb in the case of W–Pb compounds are due to an efficacious operation of the Z/r dependent diamagnetic term (higher atomic number Z of tungsten and roughly the same Mo–Pb and W–Pb distances resulting from the 4f level induced lanthanide contraction). 95Mo chemical shifts (−1838 to −2007 ppm) lie in the region typical of the molybdenum – main group metal bonded complexes but at lower fields than in the corresponding Mo–Sn compounds. It is concluded from this observation that the Z/r dependent diamagnetic contribution does not operate efficaciously for 95Mo shieldings, which are hence primarily dominated by the paramagnetic term. The nature of metal–metal interactions is discussed.

Reversible Addition of Carbon Dioxide to Main Group Metal Complexes at Temperatures about 0 °C

2021 ◽  
Author(s):  
Tatyana S. Koptseva ◽  
Vladimir G. Sokolov ◽  
Sergey Yu. Ketkov ◽  
Elena A. Rychagova ◽  
Anton V. Cherkasov ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Metal Complexes ◽  
Main Group ◽  
Group Metal ◽  
Reversible Addition ◽  
Main Group Metal

Effect of delocalization of nonbonding electron density on the stability of the M–Ccarbene bond in main group metal-imidazol-2-ylidene complexes: a computational and structural database study

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Samuel Tetteh ◽  
Albert Ofori
Keyword(s):  
Electron Density ◽  
Lone Pair ◽  
Main Group ◽  
Binding Energies ◽  
Electrostatic Model ◽  
Group Metal ◽  
Main Group Metal ◽  
Structural Database ◽  
The Stability ◽  
Lone Pair Electrons

Abstract The M–Ccarbene bond in metal (M) complexes involving the imidazol-2-ylidene (Im) ligand has largely been described using the σ-donor only model with donation of σ electrons from the sp-hybridized orbital of the carbene carbon into vacant orbitals on the metal centre. Analyses of the M–Ccarbene bond in a series of group IA, IIA and IIIA main group metal complexes show that the M-Im interactions are mostly electrostatic with the M–Ccarbene bond distances greater than the sum of the respective covalent radii. Estimation of the binding energies of a series of metal hydride/fluoride/chloride imidazol-2-ylidene complexes revealed that the stability of the M–Ccarbene bond in these complexes is not always commensurate with the σ-only electrostatic model. Further natural bond orbital (NBO) analyses at the DFT/B3LYP level of theory revealed substantial covalency in the M–Ccarbene bond with minor delocalization of electron density from the lone pair electrons on the halide ligands into antibonding molecular orbitals on the Im ligand. Calculation of the thermodynamic stability of the M–Ccarbene bond showed that these interactions are mostly endothermic in the gas phase with reduced entropies giving an overall ΔG > 0.

Comprehensive Global Energy Minimum Modeling of the Sarin−Serine Adduct

2005 ◽  
Vol 109 (2) ◽  
pp. 1006-1014 ◽  
Author(s):  
Jing Wang ◽  
Szczepan Roszak ◽  
Jiande Gu ◽  
Jerzy Leszczynski
Keyword(s):  
Energy Minimum ◽  
Global Energy ◽  
Global Energy Minimum
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