Oxidative Bond Formation and Reductive Bond Cleavage at Main Group Metal Centers: Reactivity of Five-Valence-Electron MX2 Radicals

2014 ◽  
Vol 136 (31) ◽  
pp. 10902-10905 ◽  
Author(s):  
Andrey V. Protchenko ◽  
Deepak Dange ◽  
Matthew P. Blake ◽  
Andrew D. Schwarz ◽  
Cameron Jones ◽  
...  
Keyword(s):  
Valence Electron ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Main Group ◽  
Metal Centers ◽  
Group Metal ◽  
Main Group Metal

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.

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.

Editorial: main group metal compounds

2003 ◽  
Vol 17 (1) ◽  
pp. 1-1 ◽  
Author(s):  
Peter Craig ◽  
Marcel Gielen
Keyword(s):  
Main Group ◽  
Metal Compounds ◽  
Group Metal ◽  
Main Group Metal

Addition of Sn–OiPr across a C═C Bond: Unusual Insertion of an Alkene into a Main-Group-Metal–Alkoxide Bond

2016 ◽  
Vol 35 (3) ◽  
pp. 301-302 ◽  
Author(s):  
Evgeny V. Beletskiy ◽  
Yuyang Wu ◽  
Mayfair C. Kung ◽  
Harold H. Kung
Keyword(s):  
Main Group ◽  
Metal Alkoxide ◽  
Group Metal ◽  
Main Group Metal
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