Abstract
AbstractTreatment of [Ti(OiPr)4] with trimethylsilyl triflate results in the formation of [Ti(OiPr)3(OTf)] (2) in high yield. Subsequent treatment of the triflate derivative 2 with a series of facially coordinating N3‐donor ligands results in the production of a series of charge‐separated metal alkoxide salts of the general formula [{L}Ti(OiPr)3][OTf] {L = tris(pyrazolyl)methane (3a), 1,3,5‐triethyl‐1,3,5‐triazacyclohexane (3b), 1,3,5‐tribenzyl‐1,3,5‐triazacyclohexane (3c), 1,3,5‐tris(p‐fluorobenzyl)‐1,3,5‐triazacyclohexane (3d), and 1,3,5‐tris[(1S)‐1‐phenylethyl]‐1,3,5‐triazacyclohexane (3e)}. The products were characterized by 1H and 13C NMR spectroscopy and in the case of 3a–c by single‐crystal X‐ray diffraction. Reaction of 2 with 1,3,5‐triphenyl‐1,3,5‐triazacyclohexane results in the formation of complex 4 [{L′}2Ti(OiPr)2(OTf)2], which contains two 3,4‐dihydroquinazoline ligands (L′), a result of catalytic activation of the triazacyclohexane ligands by [Ti(OiPr)3(OTf)] towards electrophilic aromatic substitution.
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