The titanium tris-anilide cation [Ti(N[[superscript t]Bu]Ar)[subscript 3]][superscript +] stabilized as its perfluoro-tetra-phenylborate salt: structural characterization and synthesis in connection with redox activity of 4,4'-bipyridine dititanium complexes
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Spinney-2015-Titanium tris-anilide.pdf
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Author(s)
Spinney, Heather A.
Clough, Christopher R.
Cummins, Christopher C.
Date Issued
February 2015
Journal
Dalton Transactions
Publisher
Royal Society of Chemistry
Citation
Spinney, Heather A., Christopher R. Clough, and Christopher C. Cummins. “The Titanium Tris-Anilide Cation [Ti(N[[superscript t]Bu]Ar)[subscript 3]][superscript +] Stabilized as Its Perfluoro-Tetra-Phenylborate Salt: Structural Characterization and Synthesis in Connection with Redox Activity of 4,4′-Bipyridine Dititanium Complexes.” Dalton Trans. 44, no. 15 (2015): 6784–6796. © 2015 Royal Society of Chemistry
Version
Final published version
Abstract
This work explores the reduction of 4,4′-bipyridine using two equivalents of the titanium(III) complex Ti(N[[superscript t]Bu]Ar)[subscript 3] resulting in formation of a black, crystalline complex, (4,4′-bipy){Ti(N[[superscript t]Bu]Ar)[subscript 3]}[subscript 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[subscript 6]F[subscript 5])[subscript 4]][superscript −] as the counter-ion. It proved possible to crystallize the salt [(4,4′-bipy){Ti(N[[superscript t]Bu]Ar)[subscript 3]}[subscript 2]][B(C[subscript 6]F[subscript 5])[subscript 4]][subscript 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[superscript 0] metal tris-amide complex, shown by X-ray crystallography to contain an intriguing pyramidal TiN[subscript 3] core geometry, namely {Ti(N[[superscript t]Bu]Ar)[subscript 3]}[superscript +], could also be isolated when using [B(C[subscript 6]F[subscript 5])[subscript 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[[superscript t]Bu]Ar)[subscript 3] has been shown to effect the reduction of substrates including halogenated organic molecules, carbonyl compounds, organic nitriles, and metal complexes.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1039/c5dt00105f
