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

대한화학회 제121회 학술발표회 및 총회 1-Electron Transfer on a (PPP)Ni Scaffold via unprecedented Metal-Ligand Cooperation

2018년 3월 7일 10시 07분 43초
INOR.P-222 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
4월 19일 (목요일) 11:00~12:30
Inorganic Chemistry
저자 및
Yeong-Eun KIM, Yunho Lee*
Department of Chemistry, Korea Advanced Institute of Science and Technology, Korea

Metal-ligand cooperation (MLC) continues to attract attention as a novel synthetic methodology to expand the role of transition metals in organometallic reactions. The ligand in MLC delivers necessary electron, proton and/or a functional group to assist metal during the chemical reactions. Although various phosphine ligands have been widely utilized in organometallic chemistry, examples of “non-innocent” phosphine ligand are relatively rare. Recently, our group reported a new type of metal-ligand cooperation with an anionic PPP ligand (PPP = P[2-PiPr2-C6H4]2). The reversible phosphide/phosphinite interconversion of a PPP ligand coupled with a 2-electron redox change of nickel (II and 0) was observed in this system. Recently a reversible 1-electron redox process of a PPP ligand coupled with P-P bond formation was studied. Divalent nickel amide species with two different amido groups (-NHMes and –NTol2) were prepared to study reversible formation of P-N and P-P bonds at a nickel center supported by a PPP ligand. While the formation of a P-N bond was successfully accomplished by addition of CO(g) to the solution of (PPP)Ni-NTol2 (Figure 1, left), the formation of a dimeric nickel(0) species, {(PPP)NiCO}2 was observed from the reaction of (PPP)Ni(NHMes) with CO(g) (Figure 1, right). The P-P bond formation was suggested as a radical pathway according to initial mechanistic studies. Activation of P-N and P-P bonds by using various reagents such as H2 will be discussed.

Figure 1. Crystral structure of (PPNTol2P)Ni(CO) (left) and {(PPP)NiCO}2 (right)