Electrophilic bis(guanidinate)titanium and bis(amidinate)tantalum complexes: Reactivity studies and solution and solid-state structural analyses | Posted on:2002-10-19 | Degree:Ph.D | Type:Thesis | University:University of California, Berkeley | Candidate:Mullins, Sarah Marie | Full Text:PDF | GTID:2461390011996091 | Subject:Chemistry | Abstract/Summary: | | Chapter 1. The reactivity of an electronically unsaturated tantalum methylidene complex supported by [TolC(NSiMe3)2] ligands is described. Electrophilic addition and olefination reactions of the Ta = CH2 functionality are reported. This complex also participates in group-transfer reactions not observed in sterically similar, but electronically saturated, analogues.; Chapter 2. The tantalum methylidene complex [TolC(NSiMe 3)2]2Ta(CH2)CH3 reacts with pyridine N-oxides to form the tantalum oxo complex [TOlC(NSiMe3)2]2Ta(O)CH3 and methylpyridines. The methylation occurs regioselectively at the unsubstituted ortho position in each pyridine N-oxide. A mechanistic study of this reaction is presented.; Chapter 3. A titanium dinitrogen complex, {lcub}[Me 2C(NiPr)2Ti{rcub}2(N2), is synthesized by reduction of the dichloride precursor, [Me2C(N iPr)2]2TiCl2. The dinitrogen complex undergoes group-transfer reactions to yield complexes containing titanium-heteroatom bonds (Ti-X and Ti = X; X = NR, O, S). The solid-state and solution structures of the compounds are discussed. This includes variable temperature and two-dimensional NMR experiments used to observe isomerization reactions and a novel guanidinate rearrangement.; Chapter 4. The synthesis of [PhC(NSiMe3) 2]2TaF3 and its conversion to alkyl and aryl derivatives is reported. The solid-state structures of these seven-coordinate compounds were determined and compared with solution data from variable temperature NMR experiments. | Keywords/Search Tags: | Complex, Tantalum, Solution, Solid-state, Chapter, Nsime | | Related items |
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