The titanium tris-anilide cation [Ti(N[(t)Bu]Ar)3](+) stabilized as its perfluoro-tetra-phenylborate salt: structural characterization and synthesis in connection with redox activity of 4,4'-bipyridine dititanium complexes

Dalton Transactions : an International Journal of Inorganic Chemistry
Heather A SpinneyChristopher C Cummins

Abstract

This work explores the reduction of 4,4'-bipyridine using two equivalents of the titanium(iii) complex Ti(N[(t)Bu]Ar)3 resulting in formation of a black, crystalline complex, (4,4'-bipy){Ti(N[(t)Bu]Ar)3}2, for which an X-ray structure determination is reported. The neutral, black, 4,4'-bipyridine-bridged bimetallic was found to be redox active, with mono- and di-anions being accessible electrochemically, and with the mono- and di-cations also being accessible chemically, and isolable, at least when using the weakly coordinating anion [B(C6F5)4](-) as the counter-ion. It proved possible to crystallize the salt [(4,4'-bipy){Ti(N[(t)Bu]Ar)3}2][B(C6F5)4]2 for a single-crystal X-ray structure investigation; in this instance it was revealed that the aromaticity of the 4,4'-bipyridine ligand, that had been disrupted upon reduction, had been regained. A rare cationic d(0) metal tris-amide complex, shown by X-ray crystallography to contain an intriguing pyramidal TiN3 core geometry, namely {Ti(N[(t)Bu]Ar)3}(+), could also be isolated when using [B(C6F5)4] as the essentially non-interacting counter-ion. This highly reactive cation should be considered as a potential intermediate in the plethora of reactions wherein Ti(N[(t)Bu]Ar)3 has be...Continue Reading

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Citations

Jun 26, 2015·Angewandte Chemie·Albert PaparoChristopher C Cummins
Jun 15, 2017·Journal of the American Chemical Society·Demyan E ProkopchukMichael T Mock
Oct 24, 2018·Chemistry : a European Journal·Albert PaparoChristopher C Cummins
Feb 13, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·A PaparoJ Okuda
Jul 28, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Albert PaparoJun Okuda

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