Reduction of Titanium(IV)-Phosphinimide Complexes: Routes to Ti(III) Dimers, Ti(IV)-Metallacycles, and Ti(II) Species

Autor:	Pingrong Wei, James E. Kickham, Silke Courtenay, Todd W. Graham, Douglas W. Stephan
Rok vydání:	2004
Předmět:	Ethylene Trimethylsilyl Stereochemistry Organic Chemistry Metallacycle Medicinal chemistry Redox Inorganic Chemistry Metal chemistry.chemical_compound chemistry Acetylene Phenylacetylene visual_art visual_art.visual_art_medium Physical and Theoretical Chemistry Diphenylacetylene
Zdroj:	Organometallics. 23:3309-3318
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om049826q
Popis:	The redox chemistry of phosphinimide-containing group IV metal complexes has been investigated. Reaction of the simple phosphinimide species CpTi(NPR3)Cl2 (R = Me 1, i-Pr 2) with Mg affords complexes formulated as [CpTiCl(μ-NPR3)]2 (R = Me 3, i-Pr 4). In contrast, CpTi(NPt-Bu3)Cl2 (5) is reduced by Mg to a putative Ti(II) species that can be intercepted by a variety of reagents including 2,3-dimethyl-1,3-butadiene, diphenylacetylene, phenylacetylene, bis(trimethylsilyl)acetylene, ethylene, and propylene to give monometallic metallacyclic complexes. In this fashion, the Ti(IV) metallacycles CpTi(NPt-Bu3)(CH2C(Me)C(Me)CH2), 6, CpTi(NPt-Bu3)(CPh)4, 7, CpTi(NPt-Bu3)(C(Ph)CHC(Ph)CH), 8, CpTi(NPt-Bu3)(η2-C2(SiMe3)2), 9, CpTi(NPt-Bu3)(CH2)4, 10, CpTi(NPt-Bu3)(CH2CHMe)2, 15, and CpTi(NPt-Bu3)(CH2)2(CPh)2, 16, were prepared. Related intramolecular formation of metallacycle complexes was achieved upon reduction of Cp‘Ti(t-Bu2(2-C6H4Ph)PN)Cl2 (Cp‘ = Cp 18, Cp* 19). The products [Cp‘Ti(NPtBu2(2-C6H4Ph)] (Cp‘ = Cp 20,...
Databáze:	OpenAIRE
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