DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Lee, Yunho | - |
dc.contributor.advisor | 이윤호 | - |
dc.contributor.author | Kim, Seji | - |
dc.contributor.author | 김세지 | - |
dc.date.accessioned | 2017-03-29T02:43:23Z | - |
dc.date.available | 2017-03-29T02:43:23Z | - |
dc.date.issued | 2016 | - |
dc.identifier.uri | http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=649771&flag=dissertation | en_US |
dc.identifier.uri | http://hdl.handle.net/10203/222060 | - |
dc.description | 학위논문(석사) - 한국과학기술원 : 화학과, 2016.2 ,[v, 60 p. :] | - |
dc.description.abstract | Recently, metal-ligand cooperation has attracted much attention in multi electron catalytic reac-tions. Especially, non-innocent behaviors of the $\pi$ -conjugated ligands have been researched as a new method-ology to expand the role of transition metal. Most of known systems employ a noninnocent motif such as aryl-substituted bis(imino)pyridine and pyridine/acridine studied by the Chirik group as well as aromatiza-tion/dearomatization to tightly couple with the redox change of metal studied by the Milstein group which is therefore known as metal-ligand cooperation. Although various phosphine ligands have been widely utilized in organometallic chemistry, examples of a noninnocent phosphine behavior are relatively rare. Recently, the Thomas group has reported a central cationic N-heterocyclic phosphenium (NHP) ligand which has a planar three-coordinate phosphorus center. We have established the interconversion between $(PPP)Ni(II) (PPP^{-} = P[2-P^{i}Pr^{2}-C_6H_4]_2^{-})$ and $(PP^{OR}P)Ni(0)$ via P-O bond formation and cleavage. Dinitrogen species, $(PP^{OMe}P)Ni(N_2)$ and ${(PP^{OMe}P)Ni}_2(\mu -N_2)$ were synthesized from the reaction of (PPP)NiCl with a methoxy anion. Under CO(g) atmosphere, a dinitrogen ligand was substituted by a carbonyl ligand at a nickel(0) center producing a monocarbonyl nickel complex $(PP^{OMe}P)Ni(CO)$. However, by exposing $CO_2(g)$, metal-ligand cooperation occurs to generate (PPP)Ni(OCOOMe) via a P-O bond cleavage followed by a migratory methoxy group transfer. In this study, the mechanisms of a reversible conversion between phosphide-nickel(II) and phosphinite-nickel(0) via P-O bond formation and cleavage and methylcarbonate generation with two equivalent of iodomethane were explained. Dinitrogen species, $(PP${OMe}P)Ni(N_2)$ and ${(PP%{OMe}P)Ni}_2(\mu -N_2) were produced from the reaction of (PPP)NiCl with a methoxy anion generated from the solution of tetramethylammonium hydroxide in methanol. Under Ar(g) atmosphere, $(PPP)Ni(II)-OR (R = Me and ^{i}Pr)$ species were generated and converted to the corresponding $(PP^{OR}P)Ni(0)-L$ by $N_2$ and CO exposure, respec-tively. To understand the reactivity of phosphide-Ni(II) species, several reactions of $(PPP)Ni(O^{i}Pr)$ with organic azides and isocyanides were conducted. | - |
dc.language | eng | - |
dc.publisher | 한국과학기술원 | - |
dc.subject | Metal-ligand cooperation | - |
dc.subject | reversible conversion | - |
dc.subject | 4-coordinated nickel complex | - |
dc.subject | nickel-carbonyl complex | - |
dc.subject | nickel-dinitrogen complex | - |
dc.subject | 금속-리간드 협력 | - |
dc.subject | 가역적 변환 | - |
dc.subject | 4배위 저원자가 니켈 착물 | - |
dc.subject | 니켈-카르보닐 착물 | - |
dc.subject | 니켈-질소 착물 | - |
dc.title | Mechanistic study of a reversible conversion between phosphinite-ni(0) and phosphide-ni(II) via unique metal-ligand cooperation | - |
dc.title.alternative | 새로운 포스핀 기반의 금속-리간드 협력 반응을 통한 포스피나이트-니켈(0)/포스파이드-니켈(II)의 가역적 변환 메카니즘 연구 | - |
dc.type | Thesis(Master) | - |
dc.identifier.CNRN | 325007 | - |
dc.description.department | 한국과학기술원 :화학과, | - |
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