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DFT studies of cobalt hydride intermediate on cobaloxime‐catalyzed H 2 evolution pathways
Author(s) -
Jiang YanKe,
Liu JianHui
Publication year - 2011
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/qua.23246
Subject(s) - bimetallic strip , hydride , chemistry , protonation , catalysis , cobalt , electrochemistry , photochemistry , gibbs free energy , computational chemistry , combinatorial chemistry , inorganic chemistry , organic chemistry , metal , electrode , thermodynamics , physics , ion
Chemical, electrochemical, and photochemical methods all had been utilized to explore proton reduction catalysis by cobaloxime complexes. It was postulated in these studies that the initial step toward making H 2 was protonation of Co I to form a Co III hydride intermediate. However, in the following steps, different results from electrochemical studies had led to both monometallic and bimetallic pathways. In this article, theoretical computation method (BP86/6‐31G*) was firstly performed on possible cobalt hydride intermediates involved in the reactive pathway of cobaloxime‐catalyzed H 2 evolution. The monometallic pathway B was excluded, both monometallic pathway A and bimetallic pathway were the possible process. However, the Gibbs free energy change for generation of H 2 following monometallic pathway A was much more negative than that following bimetallic pathway. The calculation on monometallic pathway A indicated that the main driving force of the reaction (i) came from the step of the reduction of 11 . The proton transfer steps were also studied in detail. The protonation of cobalt hydride intermediates could directly happen on the dimethylglyoximate part. All the results refer to gas‐phase calculations, not considering the solution. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011