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학술발표회초록보기

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

제116회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Transformation of Small Molecules at a Low Valent Nickel Center Supported by a Series of PEP Pincer-type Ligands

등록일
2015년 9월 4일 15시 06분 48초
접수번호
1324
발표코드
INOR.O-2 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
발표시간
목 09시 : 25분
발표형식
분과기념
발표분야
무기화학 - Oral Presentation for Young Inorganic Chemists
저자 및
공동저자
이윤호
한국과학기술원(KAIST) 화학과, Korea
The development of a greater understanding of the chemistry involved in the transition metal complex mediated activation of small molecules such as carbon dioxide and carbon monoxide is prompted in part by the need to develop agents for the utilization of such gases as a synthetic C1 source. Especially, we employ a series of PEP (E = N, P and Si) ligand to accommodate a nickel ion species in a tetracoordinate planar/tetrahedral environment. A particular study of such species is currently under investigation to show their respective roles in small-molecule transformations that include, carbon dioxide transformation for ACS/CODH chemistry and carbon monoxide conversion as a key step for hydroformylation and the Monsanto/Cativa process. In this presentation, a four coordinate (PEP)Ni-L scaffold (E = N, P or Si) where the L site is occupied by ligands such as N2, CO, CO2 and COOR will be described. The (PNP)Ni systems accommodating terminally bound CO in the three formal oxidation states (nickel(0), +1, and +2) and their reactivity toward iodoalkanes will be illustrated. The mechanistic investigations via experimental and theoretical studies will be discussed regarding the C-C bond formation at the paramagnetic nickel center. In addition, a series of CO2 adducts have been generated revealing unique binding character to a nickel center possessing a different geometry depending on the ancillary PEP ligand. With concerning the geometry and reactivity relationship, the reactivity of each Ni-CO2 adduct will be also discussed. In fact, unanticipated metal-ligand cooperation employing a (PEP)Ni scaffold will be presented in which reversible methoxy group transfer occurs between a phosphide moiety of the ligand and the nickel ion.

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