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Preparation and Structural Characterization of Metal Complexes Containing a Chelating Phenolato or Amido Ligand

The Complexes {[O3P]AlMe}Ag and {[O3P]AlMe}Tl have been synthesized and characterized successfully. The structures of {[O3P]AlMe}Ag and {[O3P]AlMe}Tl were compared with the reported {[O3P]AlMe}Li(DME)3. The 31P NMR showed that soft nature of Ag and Tl ions in {[O3P]AlMe}Ag and {[O3P]AlMe}Tl respectively is interacted with P atom of phenolato ligand and the hard Li ion did not interact with P atom. The reaction of H3[O3P] with YCl3 at RT gave [O3PH]YCl. This is confirmed by 1H NMR technique. The complexes {[O3P]Zn}2Zn(THF)2 and {[OPO]Zn}2 were prepared by the reaction of Zn salt with [O3P]3- and [OPO]2- respectively in excellent yield and characterized by 1H NMR spectroscopy. The X-ray structure of complex {[O3P]Zn}2Zn(THF)2 reveals that it is formed as trimer.
We have prepared two thallium complexes derived from diarylamido-based PNP ligands and TlOTf. 31P{1H} NMR revealed that two phosphine atoms in PNP ligand is coordinated with metal Tl center.
The palladium-catalyzed aryl amination of 1-bromo-2-chlorobenzene with 2,6-diiso- propylaniline quantitatively produces N-(2-chlorophenyl)-2,6-diisopropylaniline, H[iPrAr- NCl]. Deprotonation of H[iPrAr-NCl] with 1 equiv of n-BuLi in toluene at -35 ¢XC produced cleanly [iPrAr-NCl]Li. Subsequent recrystallization of [iPrAr-NCl]Li in diethyl ether generated the bis(ether) adduct [iPrAr-NCl]Li(OEt2)2. An X-ray study of [iPrAr-NCl]Li- (OEt2)2 showed it to be a four-coordinate species with the coordination of the chlorine atom to the lithium center.

Identiferoai:union.ndltd.org:NSYSU/oai:NSYSU:etd-1226108-142640
Date26 December 2008
CreatorsChen, Han-Sheng
ContributorsTeng-Yuan Dong, Lan-Chang Liang, Tsu-Hsin Chang, Michael 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-1226108-142640
Rightsnot_available, Copyright information available at source archive

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