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  • 02월 19일 10시 이후 : 초록수정 불가능, 일정확인 및 검색만 가능

대한화학회 제121회 학술발표회 및 총회 Synthesis and Characterization of a 4-Coordinate Cobalt(I) Dinitrogen Species

2018년 2월 6일 19시 59분 52초
INOR.P-100 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
4월 19일 (목요일) 11:00~12:30
Inorganic Chemistry
저자 및
JONGHO SO, Yunho Lee*
Department of Chemistry, Korea Advanced Institute of Science and Technology, Korea

Metal nitrene species draws much attention due to their unique reactivity in various organometallic reactions. The isolation and characterization of the late first-row transition metal complexes possessing a metal-nitrogen multiple bond are difficult because of their strong reactivity with instability relative to that of early transition metals but they are particularly of interest in our group. To investigate the role of such intermediates, it is important to understand their electronic structure which is closely related to their geometry. Although few well-characterized examples are reported, metal imido species beyond the oxo-wall such as cobalt and nickel are still rare. In order to access to such metal species, appropriate local geometry about a metal ion is crucial, thus a low coordinate metal species is under investigation as our current approach. In addition, by incorporating a silyl donor in a pincer ligand, one can achieve a strong σ-bond with late transition metal ion, thus desired stability can be attained. Here, we will present cobalt complexes supported by an anionic diphosphinosilyl MeSiP2 ligand (MeSiP2 = MeSi[2-PiPr2-C6H4]2). The precursor cobalt(II) complex was prepared by incorporating an anionic silyl coordination to cobalt(II) center via the deprotonation of a Si-H bond followed by dehalogenation. A 4-coordinate monovalent cobalt dinitrogen species, {(MeSiP2)Co}2(μ-N2) was successfully synthesized from the 1-electron reduction of (MeSiP2)CoBr. The dinuclear cobalt dinitrogen complex was characterized by various spectroscopic techniques and X-ray crystallography. Azide reagents such as PhN3 and AdN3 were introduced to access to the desired metal imido species. The details of the characterization of cobalt complexes and its reactivity toward azide will be discussed.