Synthesis and Characterization of 3-2,![]()
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- 作者：Hyunjoon Song ; Yumi Lee ; Zel-Ho Choi ; Kwangyeol Lee ; Joon T. Park ; Juhyoun Kwak ; and Moon-Gun Choi
- 刊名：Organometallics
- 出版年：2001
- 出版时间：July 9, 2001
- 年：2001
- 卷：20
- 期：14
- 页码：3139 - 3144
- 全文大小：128K
- 年卷期：v.20,no.14(July 9, 2001)
- ISSN：1520-6041
文摘
The reaction of C60 with Re3(
-H)3(CO)11(NCMe) in refluxing chlorobenzene producesRe3(-H)3(CO)9(3-
2,2,2-C60) (1) in 50% yield. Initial decarbonylation of 1 with Me3NO/MeCN followed by reaction with PPh3 in boiling chlorobenzene affords Re3(-H)3(CO)8(PPh3)(3-2,2,2-C60) (2) in a low yield (26%). Treatment of 1 with PhCH2N=PPh3 at roomtemperature gives a benzyl isocyanide substituted product Re3(-H)3(CO)8(CNCH2Ph)(3-2,2,2-C60) (3) in 53% yield. Compounds 1, 2, and 3 have been isolated as crystalline solidsand characterized by spectroscopic (infrared, mass, 1H, 31P, and 13C NMR) and analyticaldata. The structure of 3 has been determined by a single-crystal X-ray diffraction study.The C60 ligand is coordinated to the trirhenium triangle in a 3-2,2,2 bonding mode, andthe benzyl isocyanide ligand occupies an axial position of a rhenium atom. Electrochemicalproperties of 1 and 2 have been studied by cyclic voltammetry (CV) in chlorobenzene (CB)solutions. The general features of CV curves have revealed four reversible redox couples for1 and 2 in the CB potential window. The CV results suggest that a C60-mediated electrontransfer to the trirhenium center takes place in 12- species for 1 and 23- for 2.
-H)3(CO)11(NCMe) in refluxing chlorobenzene producesRe3(-H)3(CO)9(3-2,2,2-C60) (1) in 50% yield. Initial decarbonylation of 1 with Me3NO/MeCN followed by reaction with PPh3 in boiling chlorobenzene affords Re3(-H)3(CO)8(PPh3)(3-2,2,2-C60) (2) in a low yield (26%). Treatment of 1 with PhCH2N=PPh3 at roomtemperature gives a benzyl isocyanide substituted product Re3(-H)3(CO)8(CNCH2Ph)(3-2,2,2-C60) (3) in 53% yield. Compounds 1, 2, and 3 have been isolated as crystalline solidsand characterized by spectroscopic (infrared, mass, 1H, 31P, and 13C NMR) and analyticaldata. The structure of 3 has been determined by a single-crystal X-ray diffraction study.The C60 ligand is coordinated to the trirhenium triangle in a 3-2,2,2 bonding mode, andthe benzyl isocyanide ligand occupies an axial position of a rhenium atom. Electrochemicalproperties of 1 and 2 have been studied by cyclic voltammetry (CV) in chlorobenzene (CB)solutions. The general features of CV curves have revealed four reversible redox couples for1 and 2 in the CB potential window. The CV results suggest that a C60-mediated electrontransfer to the trirhenium center takes place in 12- species for 1 and 23- for 2.