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URN etd-0824108-002945 Statistics This thesis had been viewed 3326 times. Download 2239 times. Author Chien-Kai Chen Author's Email Address No Public. Department Chemical Engineering Year 2007 Semester 1 Degree Master Type of Document Master's Thesis Language zh-TW.Big5 Chinese Page Count 106 Title Synthesis and Related Reactions of Ruthenium Azido Complexes Containing a Hydrotris(pyrazolyl) borato (Tp) Ligand Keyword 1 methyleneimine azide 3-dipolar 3-dipolar azide methyleneimine 1 Abstract Methyleneimine is known to be a reactive molecule and its existence can be recognized only at low temperature by IR spectroscopy. A few metal complexes containing a methyleneimine moiety (NH=CH2) have been synthesized by the reaction of methyleneimido complex. The NH=CH2 ligand coordinates through two coordination modes; one is the N-monodentate mode(κN) of a rhenium complex and another the N, C-bidentate one (κ2N,C) of an osminum complex. Only two metal bound complexes containing methyleneimine-κN moiety have been characterized by X-ray crystallogr aphy. Herein, we describe the reaction of the complex, Tp(PPh3)(MeCN)Ru-N3(3a) with CH3I to give a methyleneimine complex of Ruthenium(II). Similarly, alkylation of Tp(PPh3)(MeCN)Ru-N3(3a) with CH3CH2Br, CH2C=C(H)CH2I, HC≡CCH2Br and C6H5CH2Br affords the ruthenium imine complexes, respectively.
The [3+2] cycloaddition reactions of alkynes, alkenes and CS2 with ruthenium azido complex [Ru]-N3 (2, [Ru] = Tp(PPh3)2Ru) have been investigated. The metal-bound heterocyclic complexes produced are triazolates [Ru]N3C2(CO2Me)2 (10) from dimethyl acetylene dicarboxylate. And reaction of 2 with tetracyanoethene affords the tetrazolato complex [Ru][C2(CN)4]N4C[C(CN)=C(CN)2](12). The structures of these complexes are all clearly established as N(2)-bound from 1H-NMR spectroscopy.
Advisor Committee Yih-Hsing Lo - advisor
Chuan-Lin Chen - co-chair
W-Fu Lee - co-chair
Files Date of Defense 2008-07-25 Date of Submission 2008-08-26