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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| Published in | Tetrahedron Vol. 51; no. 15; pp. 4321 - 4332 |
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| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
OXFORD
Elsevier Ltd
10.04.1995
Elsevier |
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| Abstract | 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. |
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| AbstractList | 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. Nitriles react with 2,3-dimethyl-1,1-bis(cyclopentadienyl)ti 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. |
| Author | Mouser, John K.M Garner, Lynnette C Hope, Håkon Weakley, Timothy J.R Doxsee, Kenneth M Juliette, Jerrick J.J |
| Author_xml | – sequence: 1 givenname: Kenneth M surname: Doxsee fullname: Doxsee, Kenneth M – sequence: 2 givenname: Lynnette C surname: Garner fullname: Garner, Lynnette C – sequence: 3 givenname: Jerrick J.J surname: Juliette fullname: Juliette, Jerrick J.J – sequence: 4 givenname: John K.M surname: Mouser fullname: Mouser, John K.M – sequence: 5 givenname: Timothy J.R surname: Weakley fullname: Weakley, Timothy J.R – sequence: 6 givenname: Håkon surname: Hope fullname: Hope, Håkon organization: Department of Chemistry, University of California, Davis, CA 95616 USA |
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| Issue | 15 |
| Keywords | VINYLIMIDO COMPLEXES INSERTION NIOBIUM NITRILES TANTALUM TITANACYCLOBUTENES MULTIPLE BONDS TITANIUM DERIVATIVES METAL-CARBON BONDS |
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| Snippet | Nitriles react with 2,3-dimethyl-1,1-bis(cyclopentadienyl)titanacyclobut-2-ene to afford either azatitanacyclohexadienes or diazatitanacyclooctatrienes. The... Nitriles react with 2,3-dimethyl-1,1-bis(cyclopentadienyl)ti to afford either azatitanacyclohexadienes or diazatitanacyclooctatrienes. The latter appear to be... |
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| Title | Titanocene imido complexes: Generation as reactive intermediates, isolation, and structural characterization |
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