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Diphenolate Phosphine Complexes of Tantalum(V) and Anilido-Phosphinimine Complexes of Aluminum(III)

The preparation and structural characterization of a series of Tantalum complexes supported by 2,2¡¦-phenylphosphinobis(4,6-di-tert-butyl- phenolate) ([OPO]2-) are described. The reaction of Li2[OPO] with TaCl5 produced yellow crystals of [OPO]2TaCl, regardless of the stoichiometry of the starting materials employed. Alkylation of [OPO]2TaCl with a variety of Grignard reagents generated [OPO]2TaR (R = Me, Et). Formation of [OPO]2TaH arise from [OPO]2TaEt undergo £]-Hydrogen elimination at 120 oC or reaction of [OPO]2TaCl with LiHBEt3. The solid-state structures of [OPO]2TaCl, [OPO]2TaOH and [OPO]2TaH and the solution of these Tantalum complexes were characterized by X-ray crystallography and multinuclear NMR spectroscopy.
A new chelating N, N ligand family incorporation an anilido- phosphinimine donor set has been designed. The ligand 1-(NHAr)-2-(PPh2=NAr)C6H4 ([NN-iPr]; Ar = 2,6-diisopropylphenyl) was prepared by Staudinger reaction with 2,6-diisopropyl- phenylazide and N-(2-diphenylphosphinopheyl)-2,6-diisopropyl-anilide. Deprotonation of H[NN-iPr] with n-BuLi in THF at -35 oC generated [NN-iPr]Li(THF). The reactions of trialkylaluminum with H[NN-iPr] produced the corresponding dialkyl complexes [NN-iPr]AlMe2 and [NN-iPr]AlEt2. The aluminum complexes were all characterized by 1H, 13C{1H}, 31P{1H}, and 27Al{1H} NMR spectroscopy. The solid-state structures of H[NN-iPr] and [NN-iPr]AlMe2 were determined by X-ray crystallography.

Identiferoai:union.ndltd.org:NSYSU/oai:NSYSU:etd-0708108-185631
Date08 July 2008
CreatorsCheng, Liang-Chien
ContributorsTsu-Hsin Chang, Lan-Chang Liang, Teng-Yuan Dong, Yen-Nan Chiang
PublisherNSYSU
Source SetsNSYSU Electronic Thesis and Dissertation Archive
LanguageCholon
Detected LanguageEnglish
Typetext
Formatapplication/pdf
Sourcehttp://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0708108-185631
Rightsnot_available, Copyright information available at source archive

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