Theoretical study of the rhenium–alkane interaction in transition metal–alkane σ-complexes
- 24 April 2007
- journal article
- research article
- Published by Proceedings of the National Academy of Sciences in Proceedings of the National Academy of Sciences
- Vol. 104 (17) , 6963-6968
- https://doi.org/10.1073/pnas.0610295104
Abstract
Metal–alkane binding energies have been calculated for [CpRe(CO)2](alkane) and [(CO)2M(C5H4)C C(C5H4)M(CO)2](alkane), where M = Re or Mn. Calculated binding energies were found to increase with the number of metal–alkane interaction sites. In all cases examined, the manganese–alkane binding energies were predicted to be significantly lower than those for the analogous rhenium–alkane complexes. The metal (Mn or Re)–alkane interaction was predicted to be primarily one of charge transfer, both from the alkane to the metal complex (70–80% of total charge transfer) and from the metal complex to the alkane (20–30% of the total charge transfer).Keywords
This publication has 61 references indexed in Scilit:
- An efficient self-consistent field method for large systems of weakly interacting componentsThe Journal of Chemical Physics, 2006
- Nature of the Transition-Metal−η2-H2 Bond in TM(CO)3X2(η2-H2) (TM = Cr, Mo, W; X = CO, PH3, PCl3, PMe3) ComplexesOrganometallics, 2002
- Understanding and exploiting C–H bond activationNature, 2002
- Organometallic alkane and noble-gas complexes in conventional and supercritical fluidsPure and Applied Chemistry, 2001
- The Effect of Alkane Structure on Rates of Photoinduced C−H Bond Activation by Cp*Rh(CO)2 in Liquid Rare Gas Media: An Infrared Flash Kinetics StudyJournal of the American Chemical Society, 1999
- Different Electronic Structure Requirements on Precursors and Transition States for the Oxidative Addition Reaction with MethaneJournal of the American Chemical Society, 1994
- Approximate density functional theory as a practical tool in molecular energetics and dynamicsChemical Reviews, 1991
- Enthalpy of carbonyl dissociation from metal hexacarbonyls M(CO)6 (M = chromium, molybdenum, tungsten) in alkane solvent: determination of intermolecular agostic bond strengthsOrganometallics, 1989
- Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitalsThe Journal of Chemical Physics, 1985
- Photochemistry of the Group 6 hexacarbonyls in low-temperature matrices. III. Interaction of the pentacarbonyls with noble gases and other matricesJournal of the American Chemical Society, 1975