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CASSCF study of bonding in NiCO and FeCO
Author(s) -
Xu Xin,
Lü Xin,
Wang Nanqin,
Zhang Qianer,
Ehara Masahiro,
Nakatsuji Hiroshi
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)72:3<221::aid-qua6>3.0.co;2-b
Subject(s) - lone pair , chemistry , metal , electron , series (stratigraphy) , molecule , computational chemistry , electronic correlation , group (periodic table) , atomic physics , chemical physics , physics , quantum mechanics , organic chemistry , paleontology , biology
A series of CASSCF calculations were performed on the ground states of NiCO and FeCO. The contributions of the σ/π interactions are checked by examining the validity of the CASSC calculation to describe the molecule with a particular choice of the active space. The calculation results substantiate that the stability of MCO is determined by a balance between π donation from the metal 3 d π to the CO 2π and repulsion between the metal σ electrons and the CO 5σ lone pair and, at the same time, emphasizes the importance of the synergistic σ/π interactions between the metal and the CO group. The relative importance of σ/π interactions depends on the nature of the metal. In the case of NiCO, it is the π donation from Ni 3 d π to CO 2π that makes the largest contribution to the formation of the NiCO bond, while in the case of FeCO, it is the correlation of σ electrons that holds the metal and CO together. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 72: 221–231, 1999