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All-electron density functional study on electronic structure, stability, and Ni-Ni bonding in polynuclear nickel complexes with bridging alkyne ligands

The method of density functional theory (DFT) has been used to study chain propagation reactions of zerovalent nickel complexes containing acetylene and σ-donor ligands. The calculations were carried out with all-electron basis sets of triple-ξ quality for the valence region and augmented with polar...

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Hauptverfasser: Koch, Jonas (VerfasserIn) , Hyla-Kryspin, Isabella (VerfasserIn) , Gleiter, Rolf (VerfasserIn) , Klettke, Thomas (VerfasserIn) , Walther, Dirk (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 11/03/1999
In: Organometallics
Year: 1999, Jahrgang: 18, Heft: 24, Pages: 4942-4948
ISSN:1520-6041
DOI:10.1021/om990277b
Online-Zugang:Resolving-System, lizenzpflichtig, Volltext: https://doi.org/10.1021/om990277b
Verlag, lizenzpflichtig, Volltext: https://pubs.acs.org/doi/abs/10.1021/om990277b
Volltext
Verfasserangaben:Jonas Koch, Isabella Hyla-Kryspin, Rolf Gleiter, Thomas Klettke, and Dirk Walther
Beschreibung
Zusammenfassung:The method of density functional theory (DFT) has been used to study chain propagation reactions of zerovalent nickel complexes containing acetylene and σ-donor ligands. The calculations were carried out with all-electron basis sets of triple-ξ quality for the valence region and augmented with polarization functions. Gradient-optimized structures are compared with known experimental data. Stationary points on the potential energy surfaces are characterized by means of calculated vibrational analyses. Computed energetics of the aggregation reaction L2Ni(C2H2) + L‘2Ni(C2H2) → L2Ni(C2H2)NiL‘2 + C2H2 (2L = C2H2, L‘ = NH3 (2a); 2L = Ni(C2H2)2, 2L‘ = C2H2 (3a); 2L = 2L‘ = C2H2 (7); 2L = C2H2, 2L‘ = none (10); L = L‘ = PH3 (11), CO (12), none (13)) together with results of natural bond orbital (NBO) population analyses are used in the discussion of metal−metal bonding and the thermodynamic stability of acetylene-bridged polynuclear Ni(0) compounds. Ni−Ni interactions in 2a, 3a, 7, and 11−13 are compared with those in the hypothetical molecule [NiL2]2 (L = PH3 (9), 2L = C2H2 (10)) as well as with the d9−d9 system of the existing (μ-C2H2)[Ni(C5H5)]2 (8).
Beschreibung:Gesehen am 10.11.2020
Beschreibung:Online Resource
ISSN:1520-6041
DOI:10.1021/om990277b

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