ISSN:
0020-7608
Schlagwort(e):
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Insertion of CO2 into the transition metal-hydride bond of [RhIIIH2(PH3)3]+, CuIH(PH3)2, and RhIH(PH3)3 was theoretically investigated with ab initio MO/MP4, SD-CI, and CCD methods. The geometries of reactants, transition states (TS), and products were optimized at the Hartree-Fock level, and then MP4, SD-CI, and CCD calculations were performed on those optimized structures. The TS of the CO2 insertion into the CuI(bond)H bond is the most reactantlike, while the TS of the CO2 insertion into the RhIII(bond)H bond is the most productlike. The activation energy (Ea) and the reaction energy (ΔE) were calculated to be 6.5 and -33.5 kcal/mol for the CO2 insertion into the Cu1(bond)H bond, 21.2 and -7.0 kcal/mol for the CO2 insertion into the Rh1(bond)H bond, and 51.3 and -1.1 kcal/mol for the Rh111(bond)H bond at the SD-CI level, where negative ΔE represents exothermicity. These results are discussed in terms of the M(bond)H bond energy and the trans-influence of the hydride ligand. © 1996 John Wiley & Sons, Inc.
Zusätzliches Material:
3 Ill.
Materialart:
Digitale Medien
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