Abstract
Titanium and zirconium derivatives of the new chelating bis(borylamido) ligand [Mes2BNCH2CH2NBMes2]2- ([Ben]2-) are prepared by treating MCl4(THF)2 (M = Ti, Zr) with (Ben)Mg(THF)2. Nitrogen−boron π-interactions in (Ben)TiCl2 and (Ben)ZrCl2(THF) result in one mesityl group in each BMes2 unit occupying space roughly above and below the MCl2 plane. (Ben)TiCl2 is smoothly alkylated by Grignard reagents in dichloromethane to give (Ben)Ti(R)Cl (R = CH2Ph, CH2CMe3) and (Ben)TiR2 (R = Me, CH2Ph), while unstable (Ben)ZrMe2 can be prepared from (Ben)ZrCl2(THF) and methyllithium in toluene. An X-ray study of (Ben)Ti(CH2Ph)Cl confirms the proposed ligand conformation and features a highly distorted “η2” benzyl ligand with a Ti−Cα−Cipso angle of only 87.0(5)°. (Ben)MMe2 complexes cleanly decompose by metalation of the ortho methyl groups from mesityl rings on different borons at room temperature (for Zr) or upon heating (for Ti). An X-ray crystal structure of (TwistBen)Zr shows it to be a dimer in which the two zircon...
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