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Pairing Energy Effects in Cyanide Complexes of CpCr III
Author(s) -
Poli Rinaldo,
Smith Kevin M.
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199912)1999:12<2343::aid-ejic2343>3.0.co;2-v
Subject(s) - steric effects , pairing , cyanide , chemistry , reactivity (psychology) , basis set , ground state , spin (aerodynamics) , crystallography , computational chemistry , stereochemistry , atomic physics , density functional theory , inorganic chemistry , physics , condensed matter physics , thermodynamics , medicine , superconductivity , alternative medicine , pathology
The steric and electronic factors responsible for the reactivity differences between CN and Cl complexes of CpCr III were examined by DFT/B3LYP computational techniques. The energy difference between quadruplet and doublet [CpCr(CN) 2 (PH 3 )], Δ E D–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 (PH 3 )] and doublet [CpCr(CN) 2 (PH 3 ) 2 ] less free PH 3 , Δ E Cr–P , is also smaller than for the Cl system. The components of Δ E Cr–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–PH 3 bond strength or steric effects.