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| Type |
Poster Presentation |
| Area |
Inorganic Chemistry |
| Room No. |
Grand Ballroom |
| Time |
10월 19일 (금요일) 11:00~12:30 |
| Code |
INOR.P-56 |
| Subject |
Unusual Co(IV)-Oxo Structure Penetrating Oxo Wall and Its Electronic Structure Elucidated by CASSCF |
| Authors |
Jun-Hyeong Kim, Mahesh Sundararajan1, Muniyandi Sankaralingam2, Mu-Hyun Baik3,*, Wonwoo Nam4,*, Sun Hee Kim5,*
Chemistry, Korea Advanced Institute of Science and Technology, Korea
1Center for Catalytic Hydrocarbon Functionalizaiton, Institute for Basic Science, India
2Department of Chemistry, National Institute of Technology Calicut, India
3Department of Chemistry, Korea Advanced Institute of Science and Technology, Korea
4Department of Chemistry, Ewha Womans University, Korea
5Western Seoul Center, Korea Basic Science Institute, Korea
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| Abstract |
The ability to generate cobalt–oxo species is of note because of the difficulty in forming high-valent metal–oxo complexes of the late transition-metal series possessing a terminal oxo ligand in a tetragonal geometry; this difficulty is referred to as the “oxo wall”. In addition, the existence of cobalt–oxo species has garnered great interest in the communities of bioinorganic and oxidation chemistry because cobalt–oxo species have been proposed as reactive intermediates in water oxidation and C–H bond activation reactions catalyzed by cobalt-based compounds. However, cobalt–oxo species have rarely been captured in the catalytic oxidation of water and organic substrates. Furthermore, few synthetic cobalt–oxo complexes have been reported in biomimetic studies and the mechanism(s) for the oxidation reactions involving cobalt–oxo species remain unclear. Therefore, elucidation of the electronic structure of cobalt–oxo species is important for understanding cobalt–oxo chemistry, and extensive efforts have been devoted to capturing and characterizing cobalt–oxo species. However, the existence of cobalt–oxo species remains a subject of debate, with the cobalt–oxyl moiety postulated as an attractive alternative to the cobalt–oxo formulation. Thus, the electronic structure of such species needs to be clarified. Herein, we report highly complex electronic structure of a quasi-stable synthetic mononuclear nonheme cobalt–oxo species, [Co(O)(TAML)]2– (TAML = tetraamido macrocyclic ligand) using Complete Active Space Self Consistent Field (CASSCF) method which is a state of the art computational tool. |
| E-mail |
kjh0910q@kaist.ac.kr |
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122nd General Meeting of the KCS