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Synthesis, characterization, and reactivity of the first hafnium alkyl complex stabilized by amidate ligands

TitleSynthesis, characterization, and reactivity of the first hafnium alkyl complex stabilized by amidate ligands
Publication TypeJournal Article
Year of Publication2005
AuthorsThomson, RK, Patrick, BO, Schafer, LL
JournalCanadian Journal of Chemistry-Revue Canadienne De Chimie
Volume83
Pagination1037-1042
Date PublishedJun
Type of ArticleArticle
ISBN Number0008-4042
Keywordsamidate, CHEMISTRY, COORDINATION CHEMISTRY, CRYSTAL, exchange processes, hafnium, HYDROAMINATION, MOLECULAR-STRUCTURE, organometallic, protonolysis, TITANIUM
Abstract

A photo and thermally stable bis(amidate)-dibenzyl complex of Hf ([(DMP)(NO)(Ph)](2)Hf(CH2Ph)(2)(THF) (2a) was formed as a monosolvated THF adduct in near quantitative yield from Hf(CH2Ph)(4) and N-2,6-dimethylphenyl(phenyl)amide (1). Isomerization between the THF-bound product and the THF-free product can be observed visually by the conversion from a red-orange product at low temperatures to a pale yellow product at high temperatures. Solid-state crystallographic characterization of the orange product confirmed its constitution as a monosolvated species. Kinetic parameters for the exchange of the THF moiety were determined from variable-temperature NMR experiments. The product of the hydrolysis of the Hf dibenzyl species by water was characterized by X-ray crystallography, and was found to be a rare tetrametallic Hf oxo cluster species (3).

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