NDLI: 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

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Clough, Christopher R. Cummins, Christopher C. Spinney, Heather A.
Description	Author Affiliation: Spinney HA ( 6-435 Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139-4307, USA. ccummins@mit.edu.)
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 $[B(C_{6}F_{5})_{4}]^{−}$ as the counter-ion. It proved possible to crystallize the salt $[(4,4′-bipy)\{Ti(N[^{t}Bu]Ar)_{3}\}_{2}][B(C_{6}F_{5})_{4}]_{2}$ 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 $TiN_{3}$ core geometry, namely $\{Ti(N[^{t}Bu]Ar)_{3}\}^{+},$ could also be isolated when using $[B(C_{6}F_{5})_{4}]$ 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 been shown to effect the reduction of substrates including halogenated organic molecules, carbonyl compounds, organic nitriles, and metal complexes.
ISSN	14779226
Issue Number	15
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-04-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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