DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Park, Joon-T. | - |
dc.contributor.advisor | 박준택 | - |
dc.contributor.author | Cho, Jeong-Ju | - |
dc.contributor.author | 조정주 | - |
dc.date.accessioned | 2011-12-13T04:26:49Z | - |
dc.date.available | 2011-12-13T04:26:49Z | - |
dc.date.issued | 1996 | - |
dc.identifier.uri | http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=105337&flag=dissertation | - |
dc.identifier.uri | http://hdl.handle.net/10203/31422 | - |
dc.description | 학위논문(박사) - 한국과학기술원 : 화학과, 1996, [ xi, 120 p. ] | - |
dc.description.abstract | 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 intramolecula... | eng |
dc.language | eng | - |
dc.publisher | 한국과학기술원 | - |
dc.subject | Cluster | - |
dc.subject | Fullerene | - |
dc.subject | Alkylidyne | - |
dc.subject | Osmium | - |
dc.subject | 오스뮴 | - |
dc.subject | 뭉치화합물 | - |
dc.subject | 풀러렌 | - |
dc.subject | 알킬리딘 | - |
dc.title | Synthesis and characterization of alkylidyne complexes of group 6 transition metals (Cr, Mo and W) | - |
dc.title.alternative | 6족 전이금속 알킬리딘의 합성과 특성에 관한 연구 ; | - |
dc.type | Thesis(Ph.D) | - |
dc.identifier.CNRN | 105337/325007 | - |
dc.description.department | 한국과학기술원 : 화학과, | - |
dc.identifier.uid | 000905536 | - |
dc.contributor.localauthor | Park, Joon-T. | - |
dc.contributor.localauthor | 박준택 | - |
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