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Density functional theory of CH bond activation by transition‐metal complex: A (η 5 ‐C 5 H 5 )ML (M=Rh, Ir; L=CH 2 , CO, SH 2 , PH 3 )+CH 4 case study
Author(s) -
Su MingDer,
Chu SanYan
Publication year - 1999
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1999)72:4<405::aid-qua24>3.0.co;2-b
Subject(s) - chemistry , enthalpy , singlet state , transition metal , density functional theory , activation energy , activation barrier , oxidative addition , transition state , computational chemistry , catalysis , thermodynamics , atomic physics , organic chemistry , physics , excited state
B3LYP/LANL2DZ calculations suggested that the singlet–triplet splitting (Δ E st = E triplet − E singlet ) of 16‐electron CpML (M=Rh, Ir; L=CH 2 , CO, SH 2 , PH 3 ) correlates well with the activation barrier as well as with the reaction enthalpy for its oxidative addition reaction into methane, that is, the smaller the Δ E st of CpML is, the lower th barrier height is and the larger the exothermicity is and, in turn, the faster the oxidative addition reaction is. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 72: 405–410, 1999