DOI: 10.1063/1.447818. On the nature of the bonding of lone pair ligands to a transition metal

On the nature of the bonding of lone pair ligands to a transition metal

10.1063/1.447818

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

We report an analysis of the interaction of the closed shell, lone pair ligands CO, NH3 and PF3 with a Cu surface. The surface is represented by one and by five atom clusters. The interaction is analyzed with the constrained space orbital variation, CSOV, method which leads to a division of the interaction into several steps and permits an unambiguous assignment for the energetic importance of each step. The importance of the σ repulsion between the ligand lone pair and the metal is demonstrated and the significance of the dipole moment of the ligand is shown. The charge rearrangements are divided into intra-unit polarization and inter-unit donation between the units. Formation of covalent chemical bonds is not particularly important for NH3; the bonding can be viewed as electrostatic and arising because of the large NH3 dipole moment. For CO and PF3, covalent bonds are formed by metal to ligand π donation; for CO, the relative importance of dπ and valence 4pπ for this bonding is examined.

Bibliography

Bagus, P. S., Hermann, K., & Bauschlicher, C. W. (1984). On the nature of the bonding of lone pair ligands to a transition metal. The Journal of Chemical Physics, 81(4), 1966â1974.

Authors 3

Paul S. Bagus (first)
Klaus Hermann (additional)
Charles W. Bauschlicher (additional)

References 34 Referenced 345

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{'key': '2024021001070077500_r3', 'first-page': '2065', 'volume': '23', 'year': '1981', 'journal-title': 'Phys. Rev. B'} / Phys. Rev. B (1981)
{'key': '2024021001070077500_r4'}
{'key': '2024021001070077500_r5'}
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{'key': '2024021001070077500_r7', 'first-page': '3374', 'volume': '78', 'year': '1983', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. (1983)
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Dates

Type	When
Created	22 years, 5 months ago (Feb. 28, 2003, 12:34 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 9:21 p.m.)
Indexed	5 months ago (March 22, 2025, 4:39 a.m.)
Issued	41 years ago (Aug. 15, 1984)
Published	41 years ago (Aug. 15, 1984)
Published Print	41 years ago (Aug. 15, 1984)

Funders 0

None

BibTeX

@article{Bagus_1984, title={On the nature of the bonding of lone pair ligands to a transition metal}, volume={81}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.447818}, DOI={10.1063/1.447818}, number={4}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Bagus, Paul S. and Hermann, Klaus and Bauschlicher, Charles W.}, year={1984}, month=aug, pages={1966–1974} }

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