Well-defined imidotitanium alkyl cations: agostic interactions, migratory insertion vs.[2+2] cycloaddition, and the first structurally authenticated AlMe(3) adduct of any transition metal alkyl cation |
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Authors: | Bolton Paul D Clot Eric Cowley Andrew R Mountford Philip |
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Institution: | Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, UK OX1 3TA. |
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Abstract: | The imidotitanium alkyl cations Ti(NtBu)(Me39]aneN3)R]+ (R = Me (3+) or CH2SiMe3(4+)) possess either a very weak alpha-agostic or beta-Si-C agostic interactions, respectively, according to 13C and 29Si NMR and DFT studies; reaction of (4+) with iPrNCNiPr gives totally selective insertion into the Ti-alkyl bond; reaction of 3+ with AlMe3 gives the first structurally characterised AlMe3 adduct of a transition metal alkyl cation (Me39]aneN3 = 1,4,7-trimethyltriazacyclononane). |
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