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

제121회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Redox-Active PPP Ligand Cooperated with a Cobalt Center through P⎯P Bond Formation and Cleavage

2018년 3월 7일 09시 55분 55초
INOR.P-221 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
4월 19일 (목요일) 11:00~12:30
Inorganic Chemistry
저자 및
Seji Kim, Yunho Lee*
Department of Chemistry, Korea Advanced Institute of Science and Technology, Korea

Phosphide containing tridentate pincer systems reveal cooperative reactivity in the presence of the 1st-row transition metal. For example, our group recently reported a unique metal⎯ligand cooperation (MLC) of a PPP (PPP = P[2-PiPr2-C6H4]2) ligand occurring at a single nickel center. By introducing a π-acidic ligand such as N2 or CO to a (PPP)nickel(II) complex, a two-electron redox change occurs at the nickel center and this reaction is nicely coupled with the transformation of phosphide to phosphinite via P⎯O/S bond formation. Thus, the group transfer reaction mediated by two-electron MLC can be established with a (PPP)Ni moiety. In order to expand current technology with a PPP system, single-electron MLC reactions are currently under investigations. In group 9, 1st-row transition metal, cobalt is our first choice to attain such open-shell type reactivity. A (PPP)Co moiety was prepared from the metalation of PPPH with CoBr2 resulted in a generation of trigonal bipyramidal (PPHP)CoBr2. Deprotonation of a cobalt(II)bromide complex with trimethylamine, in fact, induced the formation of a dimeric cobalt(I) bromide complex, {(PPP)CoBr}2 with high yield. The resulting dimeric cobalt(I) complex was generated from two 1-electron transfer reactions coupled with the formation of a P⎯P bond of the two central phosphide moieties. This P⎯P bond can be cleaved by a reduction of dinuclear cobalt(I) complex generating a central phosphide bridged cobalt(I) complex {(PPP)Co}2. Thus, the P⎯P bond formation and cleavage show a redox active character of the PPP ligand system cooperated with cobalt center. The details of one-electron redox-active processes of a (PPP)Co species through reversible P⎯P formation and cleavage will be presented.

Scheme 1.