ISSN:
1434-1948
Schlagwort(e):
Chromium
;
Cyanides
;
Density-functional calculation
;
Electronic structure
;
Spin state
;
Chemistry
;
General Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
The steric and electronic factors responsible for the reactivity differences between CN and Cl complexes of CpCrIII were examined by DFT/B3LYP computational techniques. The energy difference between quadruplet and doublet [CpCr(CN)2(PH3)], ΔED-Q, was calculated to be 21.2 kcal mol-1 with the LanL2DZ basis set. Although the high-spin configuration is still the ground state for the cyanide complex, the energy gap is 8.7 kcal mol-1 less than that found for the corresponding chloride species. The difference between quadruplet [CpCr(CN)2(PH3)] and doublet [CpCr(CN)2(PH3)2] less free PH3, ΔECr-P, is also smaller than for the Cl system. The components of ΔECr-P for CN and Cl were analyzed by calculating energies at fixed geometries in both spin states, which indicated that the influence of the cyanide group on the pairing energy was more important than changes in Cr-PH3 bond strength or steric effects.
Zusätzliches Material:
3 Ill.
Materialart:
Digitale Medien
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