Journal
ORGANOMETALLICS
Volume 31, Issue 5, Pages 1591-1594Publisher
AMER CHEMICAL SOC
DOI: 10.1021/om3001197
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Funding
- Natural Science and Engineering Research Council of Canada
- Canada Foundation for Innovation
- Queen's University
- Manitoba Research and Innovation Fund
- SABIC Petrochemicals Europe
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Reaction of [Cp2Ti(Me)(CD2Cl2)](+) (I) with 3,3-dimethyl-1-butene in oCD(2)Cl(2) at 205 K produces the alpha-agostic insertion product [(Cp2TiCH2CHMeBu)-Bu-t](+) (II), in which the chirality at C(2) induces preferential agostic binding of one of the diastereotopic alpha-H atoms; subsequent coordination of ethyl ether to II leaves the alpha-agostic interaction weakened but intact. On warming, II undergoes beta-hydrogen elimination and the resulting hydride reacts further with excess 3,3-dimethyl-1-butene to form the beta-agostic species [(Cp2TiCH2CH2Bu)-Bu-t](+). NMR data and calculated (DFT) energies support the assignments.
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