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The titanocene imido complex 2 with a m-terphenyl moiety is synthesized by reacting Cp2Ti(η2-Me3SiC2SiMe3) (1) with m-terphenyl azide. Subsequent reactivity studies with tetrahydrofuran, pyridine, and nitriles verify that these substrates act as two-electron donors, thus binding end-on to the titanium center to give the donor-stabilized titanocene imides 3a,b and 4a-c. Given the potential of the titanium center to act as an electron acceptor, 2 was reacted with phosphine oxides (OPEt3/OPPh3) according to the Gutmann-Beckett method to get information about the Lewis acidity of 2 and to yield 5a,b. Complex 5a is one of the rare examples of structurally characterized titanium complexes with an η1-bound cyclopentadienyl ligand. Further insights into the Lewis acidity of 2 were obtained from the nitrile adducts 4a-c through IR spectroscopy and NMR spectroscopy (δ(19F) and 1JC,F employing 4-fluorobenzontrile). In reactions of 2 with terminal alkynes, the respective titanium amido acetylides 6a,b were obtained, whereas reactions with internal alkynes demonstrate that 2 is not very prone to undergoing [2 + 2] cycloaddition reactions.

Original publication




Journal article



Publication Date





3232 - 3239