Computational Assessment of the Effect of σ−π Bonding Synergy and Reorganization Energies on Experimental Trends in Rhodium−Phosphine Bond Enthalpies

Autor:	Chris E. Wozniak, Kenneth Gene Moloy, and Jamal Uddin, Steven Feldgus, Clark R. Landis
Rok vydání:	2000
Předmět:	Series (mathematics) Chemistry Bond Organic Chemistry Enthalpy chemistry.chemical_element Nanotechnology Rhodium Inorganic Chemistry chemistry.chemical_compound Physical chemistry Physical and Theoretical Chemistry Bond energy Phosphine
Zdroj:	Organometallics. 19:4878-4886
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om000544+
Popis:	Via a series of systematic density functional (B3LYP/LANL2DZ) computational experiments, we have examined the origin of opposing Rh−PR3 bond enthalpy trends involving two different square-planar Rh(I) complexes with a series of different π-accepting phosphines (Huang, J. K.; Haar, C. M.; Nolan, S. P.; Marshall, W. J.; Moloy, K. G. J. Am. Chem. Soc. 1998, 120, 7806). Computational results rule out reorganization energies as the cause of the contradictory trends in thermodynamic analyses of metal−ligand bonding. Rather, calculations show that synergy of σ-donor and π-acceptor ligands linked to a metal is pivotal for interpreting the contradictory trends in Rh−P bond enthalpies. We conclude that metal−phosphine bond energies cannot be regarded as intrinsic, universal, or transferable.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::8bdea2c72f63369b62e1aa821b68026b https://doi.org/10.1021/om000544+ Zobrazit plný text záznamu