Metal atom reactions of cobalt with cyclopentadiene and alkynes: synthesis of structurally novel organometallic complexes

1980 ◽  
Vol 19 (5) ◽  
pp. 1132-1141 ◽  
Author(s):  
Michael B. Freeman ◽  
Laurence W. Hall ◽  
Larry G. Sneddon
Keyword(s):  
Metal Atom ◽  
Organometallic Complexes ◽  
Metal Atom Reactions

Metal atom reactions with fluorocarbons. 9. Preparation and spectral analyses of (perfluoroalkyl)- and (perfluoroaryl)palladium halides

1980 ◽  
Vol 19 (12) ◽  
pp. 3719-3724 ◽  
Author(s):  
Kenneth J. Klabunde ◽  
Bruce B. Anderson ◽  
Kent Neuenschwander
Keyword(s):  
Metal Atom ◽  
Spectral Analyses ◽  
Metal Atom Reactions

Metal atom reactions with fluorocarbons. I. Nonsolvated fluoroorganic zinc compounds

1972 ◽  
Vol 94 (3) ◽  
pp. 999-1000 ◽  
Author(s):  
Kenneth J. Klabunde ◽  
M. Scott Key ◽  
J. Y. F. Low
Keyword(s):  
Metal Atom ◽  
Zinc Compounds ◽  
Metal Atom Reactions

scholarly journals Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes

2020 ◽  
Vol 118 (1) ◽  
pp. e2019265118
Author(s):  
Qingyun Wan ◽  
Jun Yang ◽  
Wai-Pong To ◽  
Chi-Ming Che
Keyword(s):  
Metal Complex ◽  
Metal Atom ◽  
Density Functional ◽  
Relativistic Effect ◽  
Closed Shell ◽  
Organometallic Complexes ◽  
Orbital Interaction ◽  
Orbital Hybridization ◽  
Metal Metal ◽  
Pauli Repulsion

Metallophilicity is defined as the interaction among closed-shell metal centers, the origin of which remains controversial, particularly for the roles of spd orbital hybridization (mixing of the spd atomic orbitals of the metal atom in the molecular orbitals of metal complex) and the relativistic effect. Our studies reveal that at close M–M′ distances in the X-ray crystal structures of d8 and d10 organometallic complexes, M–M′ closed-shell interactions are repulsive in nature due to strong M–M′ Pauli repulsion. The relativistic effect facilitates (n + 1)s-nd and (n + 1)p-nd orbital hybridization of the metal atom, where (n + 1)s-nd hybridization induces strong M–M′ Pauli repulsion and repulsive M–M′ orbital interaction, and (n + 1)p-nd hybridization suppresses M–M′ Pauli repulsion. This model is validated by both DFT (density functional theory) and high-level coupled-cluster singles and doubles with perturbative triples computations and is used to account for the fact that the intermolecular or intramolecular Ag–Ag′ distance is shorter than the Au–Au′ distance, where a weaker Ag–Ag′ Pauli repulsion plays an important role. The experimental studies verify the importance of ligands in intermolecular interactions. Although the M–M′ interaction is repulsive in nature, the linear coordination geometry of the d10 metal complex suppresses the L–L′ (ligand–ligand) Pauli repulsion while retaining the strength of the attractive L–L′ dispersion, leading to a close unsupported M–M′ distance that is shorter than the sum of the van der Waals radius (rvdw) of the metal atoms.

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