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  • 09월 08일 17시 이후 : 초록수정 불가능, 일정확인 및 검색만 가능

제116회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Biomimetic Reactivity of Metal-O2 Adducts

등록일
2015년 8월 25일 15시 07분 47초
접수번호
0206
발표코드
INOR2-3 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
발표시간
금 09시 : 50분
발표형식
심포지엄
발표분야
무기화학 - Recent Trends in Bioinorganic Chemistry
저자 및
공동저자
조재흥
대구경북과학기술원(DGIST) 신물질과학, Korea
The reactivity of mononuclear metal-O2 adducts has long fascinated researchers in many areas due to the significance of diverse biological and catalytic processes. Herein, a set of nickel(III)-peroxo complexes bearing tetraazamacrocyclic ligands, [Ni(TBDAP)(O2)]+ and [Ni(CHDAP)(O2)]+, were prepared by reacting [Ni(TBDAP)(NO3)]+ and [Ni(CHDAP)(NO3)]+, respectively, with H2O2 in the presence of triethylamine. The mononuclear nickel(III)-peroxo intermediates were fully characterized by various physicochemical methods, such as UV-vis, ESI-MS, resonance Raman, EPR and X-ray analysis. The spectroscopic and structural characterization clearly shows that the NiO2 cores are almost identical where the peroxo ligand is bound in a side-on fashion. However, the different steric properties of the supporting ligands were confirmed by X-ray crystallography where the CHDAP ligand gives enough space around the Ni core compared to the TBDAP ligand. In the aldehyde deformylation reaction, the nucleophilic reactivity of the nicke(III)-peroxo complexes was highly dependent on the steric properties of the macrocyclic ligands, with the reactivity order of [Ni(TBDAP)(O2)]+ < [Ni(CHDAP)(O2)]+. This result provides fundamental insight into the mechanism of the structure-reactivity relationship of metal-peroxo intermediates.

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