Pyridonate-Supported Titanium(III). Benzylamine as an Easy-To-Use Reductant

Pyridonate-Supported Titanium(III). Benzylamine as an Easy-To-Use Reductant. Chong, E., Xue, W., Storr, T., Kennepohl, P., & Schafer, L., L. Organometallics, 34(20):4941-4945, 10, 2015.

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The reaction of bis(3-phenyl-2-pyridonate)Ti- (NMe2)2 with excess benzylamine leads to an unexpected reduction of the metal center from Ti(IV) to Ti(III). The reduced titanium species was isolated and revealed as tris(3- phenyl-2-pyridonate)Ti(NH2Bn)2. Ammonia and N-benzyl-1- phenylmethanimine are released as byproducts of the reaction, thereby confirming benzylamine as a mild reductant. This new pyridonate-supported titanium(III) complex has been fully characterized, and experimental data and theoretical calculations confirm a d1 metal center with no ligand-based radical character. This Ti(III) complex does not react with aminoalkenes, suggesting that radical species are not viable intermediates for the hydroaminoalkylation or hydroamination reaction.

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 title = {Pyridonate-Supported Titanium(III). Benzylamine as an Easy-To-Use Reductant},
 type = {article},
 year = {2015},
 keywords = {EPR},
 pages = {4941-4945},
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 abstract = {The reaction of bis(3-phenyl-2-pyridonate)Ti- (NMe2)2 with excess benzylamine leads to an unexpected reduction of the metal center from Ti(IV) to Ti(III). The reduced titanium species was isolated and revealed as tris(3- phenyl-2-pyridonate)Ti(NH2Bn)2. Ammonia and N-benzyl-1- phenylmethanimine are released as byproducts of the reaction, thereby confirming benzylamine as a mild reductant. This new pyridonate-supported titanium(III) complex has been fully characterized, and experimental data and theoretical calculations confirm a d1 metal center with no ligand-based radical character. This Ti(III) complex does not react with aminoalkenes, suggesting that radical species are not viable intermediates for the hydroaminoalkylation or hydroamination reaction.},
 bibtype = {article},
 author = {Chong, Eugene and Xue, Wei and Storr, Tim and Kennepohl, Pierre and Schafer, Laurel L.},
 doi = {10.1021/acs.organomet.5b00469},
 journal = {Organometallics},
 number = {20}
}

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