Titanium imido complexes containing 1,3,5-triazacyclohexane ligands
The syntheses of the 1,3,5-trimethyl- and tri-tert-butyl-1,3,5-triazacyclohexane-supported imido complexes [M(NR)(R′ 3tach)Cl 2] (M = Ti or Zr (NMR only); R = Bu t or 2,6-C 6H 3Pr...
| Main Authors: | , , , |
|---|---|
| Format: | Journal article |
| Language: | English |
| Published: |
2000
|
| _version_ | 1797094066239832064 |
|---|---|
| author | Wilson, P Blake, A Mountford, P Schroder, M |
| author_facet | Wilson, P Blake, A Mountford, P Schroder, M |
| author_sort | Wilson, P |
| collection | OXFORD |
| description | The syntheses of the 1,3,5-trimethyl- and tri-tert-butyl-1,3,5-triazacyclohexane-supported imido complexes [M(NR)(R′ 3tach)Cl 2] (M = Ti or Zr (NMR only); R = Bu t or 2,6-C 6H 3Pr i2; R′ = Me or Bu t) are reported, along with that of the thermally robust dibenzyl derivative [Ti(NBu t)(Me 3tach)(CH 2Ph) 2]. The tert-butylimido ligand in [Ti(NBu t)(Me 3tach)Cl 2] undergoes exchange with ArNH 2 (Ar = 4-C 6H 4Me or 2,6-C 6H 4Me or 2,6-C 6H 3Pr i2) to form the corresponding arylimides [Ti(NAr)(Me 3tach)Cl 2]. The Me 3tach ring in [Ti(NR)(Me 3tach)Cl 2] undergoes slow exchange with Bu t3tach or Me 3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) to give the ring-exchanged products [Ti(NR)(Bu t3tach)Cl 2] and [Ti(NR)(Me 3tacn)Cl 2], respectively. The complexes [Ti(NR)(Me 3tach)X 2] (R = Bu t or 2,6-C 6H 3Pr i2; X = Cl or CH 2Ph) exhibit room-temperature dynamic NMR behaviour via an unusual trigonal twist of the facially coordinated Me 3tach ligand, and the activation parameters for these processes have been measured and are discussed. The X-ray structures of [Ti(NR)(Bu t3tach)Cl 2] (R = Bu t or 2,6-C 6H 3Pr i2) and [Ti(NBu t)(Me 3tach)(X) 2] [X= Cl or CH 2Ph) are reported. Me 3tach and Bu t3tach = 1,3,5-trimethyl- and tri-tert-butyl-1,3,5-triazacyclohexane, respectively. © 2000 Elsevier Science S.A. All rights reserved. |
| first_indexed | 2024-03-07T04:08:59Z |
| format | Journal article |
| id | oxford-uuid:c72f10a4-43fb-46a1-bef3-5ed5c6adc323 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T04:08:59Z |
| publishDate | 2000 |
| record_format | dspace |
| spelling | oxford-uuid:c72f10a4-43fb-46a1-bef3-5ed5c6adc3232022-03-27T06:43:08ZTitanium imido complexes containing 1,3,5-triazacyclohexane ligandsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:c72f10a4-43fb-46a1-bef3-5ed5c6adc323EnglishSymplectic Elements at Oxford2000Wilson, PBlake, AMountford, PSchroder, MThe syntheses of the 1,3,5-trimethyl- and tri-tert-butyl-1,3,5-triazacyclohexane-supported imido complexes [M(NR)(R′ 3tach)Cl 2] (M = Ti or Zr (NMR only); R = Bu t or 2,6-C 6H 3Pr i2; R′ = Me or Bu t) are reported, along with that of the thermally robust dibenzyl derivative [Ti(NBu t)(Me 3tach)(CH 2Ph) 2]. The tert-butylimido ligand in [Ti(NBu t)(Me 3tach)Cl 2] undergoes exchange with ArNH 2 (Ar = 4-C 6H 4Me or 2,6-C 6H 4Me or 2,6-C 6H 3Pr i2) to form the corresponding arylimides [Ti(NAr)(Me 3tach)Cl 2]. The Me 3tach ring in [Ti(NR)(Me 3tach)Cl 2] undergoes slow exchange with Bu t3tach or Me 3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) to give the ring-exchanged products [Ti(NR)(Bu t3tach)Cl 2] and [Ti(NR)(Me 3tacn)Cl 2], respectively. The complexes [Ti(NR)(Me 3tach)X 2] (R = Bu t or 2,6-C 6H 3Pr i2; X = Cl or CH 2Ph) exhibit room-temperature dynamic NMR behaviour via an unusual trigonal twist of the facially coordinated Me 3tach ligand, and the activation parameters for these processes have been measured and are discussed. The X-ray structures of [Ti(NR)(Bu t3tach)Cl 2] (R = Bu t or 2,6-C 6H 3Pr i2) and [Ti(NBu t)(Me 3tach)(X) 2] [X= Cl or CH 2Ph) are reported. Me 3tach and Bu t3tach = 1,3,5-trimethyl- and tri-tert-butyl-1,3,5-triazacyclohexane, respectively. © 2000 Elsevier Science S.A. All rights reserved. |
| spellingShingle | Wilson, P Blake, A Mountford, P Schroder, M Titanium imido complexes containing 1,3,5-triazacyclohexane ligands |
| title | Titanium imido complexes containing 1,3,5-triazacyclohexane ligands |
| title_full | Titanium imido complexes containing 1,3,5-triazacyclohexane ligands |
| title_fullStr | Titanium imido complexes containing 1,3,5-triazacyclohexane ligands |
| title_full_unstemmed | Titanium imido complexes containing 1,3,5-triazacyclohexane ligands |
| title_short | Titanium imido complexes containing 1,3,5-triazacyclohexane ligands |
| title_sort | titanium imido complexes containing 1 3 5 triazacyclohexane ligands |
| work_keys_str_mv | AT wilsonp titaniumimidocomplexescontaining135triazacyclohexaneligands AT blakea titaniumimidocomplexescontaining135triazacyclohexaneligands AT mountfordp titaniumimidocomplexescontaining135triazacyclohexaneligands AT schroderm titaniumimidocomplexescontaining135triazacyclohexaneligands |