Titanocene imido complexes: Generation as reactive intermediates, isolation, and structural characterization

Nitriles react with 2,3-dimethyl-1,1-bis(cyclopentadienyl)titanacyclobut-2-ene to afford either azatitanacyclohexadienes or diazatitanacyclooctatrienes. The latter appear to be formed via the intermediacy of butadienylimido complexes, which can be intercepted by the addition of trimethylphosphine. B...

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Bibliographic Details
Published inTetrahedron Vol. 51; no. 15; pp. 4321 - 4332
Main Authors Doxsee, Kenneth M, Garner, Lynnette C, Juliette, Jerrick J.J, Mouser, John K.M, Weakley, Timothy J.R, Hope, Håkon
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier Ltd 10.04.1995
Elsevier
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
VINYLIMIDO COMPLEXES
INSERTION
NIOBIUM
NITRILES
TANTALUM
TITANACYCLOBUTENES
MULTIPLE BONDS
TITANIUM
DERIVATIVES
METAL-CARBON BONDS
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Summary:Nitriles react with 2,3-dimethyl-1,1-bis(cyclopentadienyl)titanacyclobut-2-ene to afford either azatitanacyclohexadienes or diazatitanacyclooctatrienes. The latter appear to be formed via the intermediacy of butadienylimido complexes, which can be intercepted by the addition of trimethylphosphine. Bis(cyclopentadienyl)titanium bis(trimethylphosphine) undergoes ligand substitution reactions with nitriles. Loss of trimethylphosphine from the 2,4,6-trimethylbenzonitrile complex appears to lead to reductive coupling of the nitrile, affording a dimeric imido complex. Treatment of titanacyclobutenes with nitriles affords reactive titanocene imido complexes. Trapping with trimethylphosphine has permitted their isolation and structural characterization.
ISSN:0040-4020
1464-5416
DOI:10.1016/0040-4020(94)01122-G