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Please use this identifier to cite or link to this item: http://ir.ncue.edu.tw/ir/handle/987654321/14763

Title: Synthesis and Characterization Five-coordinate Molybdenum Compounds Bearing Bi-or Tridentate Substituted Pyrrole Ligands: Molecular Structures of {Mo(NC6H3Pri-2,6)2R[NC4H3(CH2NMe2)-2]} and {Mo(NC6H3Pri-2,6)2Cl[NC4H2(CH2NMe2)-2,5]}, where R=Cl, Me, Bu
Authors: Huang, Jui-Hsien;Chen, Hsing-Jen;Hsieh, Chung-Ching;Lee, Gene-Hsiang;Peng, Shie-Ming
Contributors: 化學系
Keywords: Pyrrole;Five coordinate;Molybdenum compounds;Bidentate;Tridentate
Date: 2001-09
Issue Date: 2012-12-10T01:39:23Z
Publisher: Elsevier
Abstract: Reacting [Mo(NC6H3Pri2-2,6)2Cl2(dme)] with 1 equiv. of Li [NC4H3(CH2NMe2)-2] in diethyl ether at −78 °C yields a red crystalline solid of {Mo(NC6H3Pri2-2,6)2Cl[NC4H3(CH2NMe2)-2]} 1 in 86% yield. Alkylation of 1 with RLi in diethyl ether generates {Mo(NC6H3Pri2-2,6)2R[NC4H3(CH2NMe2)-2]} (2a, R=Me; 2b, R=Bu) in high yield. Similarly, reacting [Mo(NC6H3Pri2-2,6)2Cl2(dme)] with 1 equiv. of Li[NC4H2(CH2NMe2)2-2,5] in diethyl ether at −78 °C affords dark red crystals of {Mo(NC6H3Pri2-2,6)2Cl[NC4H2(CH2NMe2)2-2,5]} 3 in 92% yield, in which one NMe2 unit of the pyrrole ligand of 3 coordinates to molybdenum whilst the other one dangles outside the coordination sphere. Variable-temperature 1H NMR study of 3 reveals fluxional behavior of the two NMe2 units of the pyrrole ligand. The activation energy of the fluxionality has been determined as ΔG≠=10.5 kcal mol−1. Compounds 1, 2a, 2b and 3 have been characterized by NMR spectroscopy and X-ray crystallography.
Relation: Inorg. Chim. Acta., 321(1-2): 142-148
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