Computational analysis of M-O covalency in M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, U)

A series of compounds M(OC6H5)4 (M = Ti, Zr, Hf, Ce, Th, U) is studied with hybrid density functional theory, to assess M-O bond covalency. The series allows for the comparison of d and f element compounds that are structurally similar. Two well-established analysis methods are employed: Natural Bon...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2019-02, Vol.48 (9), p.2939-2947
Main Authors: Berryman, Victoria E J, Whalley, Zoë J, Shephard, Jacob J, Ochiai, Tatsumi, Price, Amy N, Arnold, Polly L, Parsons, Simon, Kaltsoyannis, Nikolas
Format: Article
Language:English
Subjects:
Covalence
Deformation
Density functional theory
Electron density
Hafnium
Kinetic energy
Quantum theory
Titanium
Transition metals
Zirconium
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Summary:A series of compounds M(OC6H5)4 (M = Ti, Zr, Hf, Ce, Th, U) is studied with hybrid density functional theory, to assess M-O bond covalency. The series allows for the comparison of d and f element compounds that are structurally similar. Two well-established analysis methods are employed: Natural Bond Orbital and the Quantum Theory of Atoms in Molecules. A consistent pattern emerges; the U-O bond is the most covalent, followed by Ce-O and Th-O, with those involving the heavier transition metals the least so. The covalency of the Ti-O bond differs relative to Ce-O and Th-O, with the orbital-based method showing greater relative covalency for Ti than the electron density-based methods. The deformation energy of r(M-O) correlates with the d orbital contribution from the metal to the M-O bond, while no such correlation is found for the f orbital component. f orbital involvement in M-O bonding is an important component of covalency, facilitating orbital overlap and allowing for greater expansion of the electrons, thus lowering their kinetic energy.
ISSN:1477-9226
1477-9234
DOI:10.1039/c8dt05094e