서지주요정보
Synthesis and characterization of alkylidyne complexes of group 6 transition metals (Cr, Mo and W) = 6족 전이금속 알킬리딘의 합성과 특성에 관한 연구
서명 / 저자 Synthesis and characterization of alkylidyne complexes of group 6 transition metals (Cr, Mo and W) = 6족 전이금속 알킬리딘의 합성과 특성에 관한 연구 ; Synthesis and characterization of triosmium cluster complexes of $C_{60}$ = 풀러렌-트리오스 뮴 뭉치화합물의 합성과 특성에 관한 연구 / Jeong-Ju Cho.
발행사항 [대전 : 한국과학기술원, 1996].
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8006650

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학술문화관(문화관) 보존서고

DCH 96001

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초록정보

The N,N,N',N'-tetramethylethylenediamine (TMEDA) substituted alkylidyne complexes, $Br(CO)_2$(tmeda)M≡CTol [M=Cr(1), Mo(2), W(3)], have been prepared from the reaction of $Br(CO)_4$M≡CTol with TMEDA. Complexes 1,2 and 3 exist as two diastereomers in solution. One of the diastereomers, trans,cis-$Br(CO)_2$(tmeda) Cr≡CTol (1a), has been structurally characterized via a single crystal X-ray diffraction study and the other, cis,trans-1b, charactrized by IR and NMR spectroscopic methods. An efficient synthetic method of chromium alkylidyne complexes, $Cp(CO)_2$Cr≡CTol (4) and Tp*$(CO)_2$Cr≡CTol (5) [Tp*=hydrotris (3,5-dimethyl pyrazol-1-yl)borato], has been developed. These complexes have been prepared from the reaction of $Br(CO)_2$(py)_2Cr≡CTol (6) with NaCp and KTp* in good yields. The first cluster - bound $C_{60}$ derivatives, $Os_3(CO)_{11}(\eta^2-C_{60})$ (7), $Os_3(CO)_{10}(NCMe)(η^2-C_{60})$ (10) have been synthesized. Spectroscopic data (IR and NMR) support that the $C_{60}$ ligand is coordinated to an osmium atom at an equatorial site of the triosmium cluster. Complex 7 has been characterized by a single crystal X-ray diffraction study, which shows the $η^2$-binding of the $C_{60}$ ligand to an osmium atom at a 6-6 fullerene double bond. Fluxional behavior of 8 in solution has been investigated by variable temperature $^{13}C$ NMR, which reveals the restricted cyclic in-plane motion of carbonyl and $C_{60}$ ligands. Electrochemistry of $C_{60}$-triosmium complexes (7, 9, and 10) has been studied by cyclic voltammetry. The first one-electron reductions of 7 and 9 are localized at the coordinated $C_{60}$ ligand. The electrons accepted via $C_{60}$ are transferred intramolecularly to the triosmium center, which is supported by the observation that the second and third reduction potiontials of 7 and 9 are more positived than those of $C_{60}$. The first and second reduction potential is more positive than that of $C_{60}$. This indicates that intramolecular electron transfer may occur after two-electron reductions of 10. As the phosphine ligands substute the carbonyl ligands, the reduction potentials of the $C_{60}$-triosmium complexes shift to a more negative region due to the electron-donor effect of the phosphine ligands.

서지기타정보

서지기타정보
청구기호 {DCH 96001
형태사항 xi, 120 p. : 삽도 ; 26 cm
언어 영어
일반주기 저자명의 한글표기 : 조정주
지도교수의 영문표기 : Joon-T. Park
지도교수의 한글표기 : 박준택
학위논문 학위논문(박사) - 한국과학기술원 : 화학과,
서지주기 Reference : p. 111-113
주제 Alkylidyne
Fullerene
Cluster
Osmium
$C_{60}$
알킬리딘
풀러렌
뭉치화합물
오스뮴
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