| dc.contributor |
Massachusetts Institute of Technology. Department of Chemistry |
|
| dc.contributor |
Spinney, Heather A. |
|
| dc.contributor |
Clough, Christopher R. |
|
| dc.contributor |
Cummins, Christopher C. |
|
| dc.creator |
Spinney, Heather A. |
|
| dc.creator |
Clough, Christopher R. |
|
| dc.creator |
Cummins, Christopher C. |
|
| dc.date |
2015-05-04T14:14:37Z |
|
| dc.date |
2015-05-04T14:14:37Z |
|
| dc.date |
2015-02 |
|
| dc.date |
2015-01 |
|
| dc.date.accessioned |
2023-03-01T18:08:00Z |
|
| dc.date.available |
2023-03-01T18:08:00Z |
|
| dc.identifier |
1477-9226 |
|
| dc.identifier |
1477-9234 |
|
| dc.identifier |
http://hdl.handle.net/1721.1/96889 |
|
| dc.identifier |
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 |
|
| dc.identifier |
https://orcid.org/0000-0003-2568-3269 |
|
| dc.identifier.uri |
http://localhost:8080/xmlui/handle/CUHPOERS/278873 |
|
| dc.description |
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. |
|
| dc.description |
Syngenta |
|
| dc.format |
application/pdf |
|
| dc.language |
en_US |
|
| dc.publisher |
Royal Society of Chemistry |
|
| dc.relation |
http://dx.doi.org/10.1039/c5dt00105f |
|
| dc.relation |
Dalton Transactions |
|
| dc.rights |
Creative Commons Attribution |
|
| dc.rights |
http://creativecommons.org/licenses/by/3.0/ |
|
| dc.source |
Royal Society of Chemistry |
|
| dc.title |
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 |
|
| dc.type |
Article |
|
| dc.type |
http://purl.org/eprint/type/JournalArticle |
|