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DFT Studies on the Mechanism of Alcohol Oxidation Catalyzed by the Ni III /bipy Complex
Author(s) -
Cheng Lin,
Li Jie,
Li Jianing,
Zheng Hongna,
Wu Zhijian
Publication year - 2012
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/ejic.201200006
Subject(s) - catalysis , chemistry , alcohol , catalytic cycle , medicinal chemistry , reaction mechanism , homo/lumo , alcohol oxidation , photochemistry , inorganic chemistry , organic chemistry , molecule
On the basis of our previous DFT calculations on the catalytic reaction cycle catalyzed by Cu II /bipy (2,2′‐bipyridine), a new Ni III /bipy catalyst has been designed. By examining the mechanism of alcohol oxidation catalyzed by the Ni III /bipy catalyst, it was found that the barrier calculated for the rate‐determining step (16.3 kcal/mol) is 12.2 kcal/mol lower than that for the corresponding Cu II /bipy catalyst. This indicates that the Ni III /bipy catalyst might be a potential catalyst for green alcohol oxidation. In addition, the reasons for the higher activity of the Ni III /bipy catalyst relative to the Cu II /bipy catalyst are discussed. It was found that the unoccupied Ni III (d 7 ) d x 2 – y 2orbital might be the reason for the higher activity of the Ni III /bipy catalyst. The singly occupied Ni III (d 7 ) d z 2orbital plays a very important role in producing the final product (CH 3 CHO) in the absence of an oxidation auxilliary.