The boron-bridged constrained geometry titanium complexes [Ti{η5:η1-(C5H4)B(NR2)NPh}(NMe2)2]
[R =
iPr (3), SiMe3
(4)] and [Ti{η5:η1-(C9H6)B(NiPr2)NPh}(NMe2)2]
(12) have been prepared in good yields by amine elimination reaction from [Ti(NMe2)4]. Subsequent deamination–chlorination with excess Me3SiCl yielded the corresponding dichloro-complexes (5, 6, 13). Reaction of the analogous ligand precursors (C5H5)B(NiPr2)N(H)R (R = Cy, tBu) with [Ti(NMe2)4] did not result in the expected bridged compounds, but rather in the half-sandwich complexes [Ti{(η5-C5H4)B(NiPr2)N(H)R}(NMe2)3]
[R = Cy (9), tBu (10)]. All compounds were fully characterised by means of multinuclear NMR spectroscopy. Thorough investigation of substituent effects was achieved by comparative X-ray diffraction studies on complexes 3, 5, 6 and 12.
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