Titanium imido complexes with tetraaza macrocyclic ligands
Tetraaza macrocycle-supported tert-bulyl titanium imido complexes [Ti(NBut)(Mentaa)] (n = 4 2 or 8 3; H2Mentaa = 6,8,15,17-tetra- or 2,3,6,8,11,12,17,18-octa-methyl-5,14-dihydrodibenzo[b,i][1,4,8,11] tetraazacyclotetradecine, respectively), [Ti(NBut)(Me4taen)] (5, H2Me4taen = 5,7,12,14-tetramethyl-1...
| Main Authors: | , , |
|---|---|
| Format: | Journal article |
| Language: | English |
| Published: |
1998
|
| _version_ | 1826278189426540544 |
|---|---|
| author | Swallow, D McInnes, J Mountford, P |
| author_facet | Swallow, D McInnes, J Mountford, P |
| author_sort | Swallow, D |
| collection | OXFORD |
| description | Tetraaza macrocycle-supported tert-bulyl titanium imido complexes [Ti(NBut)(Mentaa)] (n = 4 2 or 8 3; H2Mentaa = 6,8,15,17-tetra- or 2,3,6,8,11,12,17,18-octa-methyl-5,14-dihydrodibenzo[b,i][1,4,8,11] tetraazacyclotetradecine, respectively), [Ti(NBut)(Me4taen)] (5, H2Me4taen = 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraene) and [Ti(NBut)(TTP)] (6, H2TTP = 5,10,15,20-tetratolylporphyrin) together with the N2O2-donor Schiff base analogue [Ti(NBut)(acen)] (7, H2acen = 4,9-dimethyl-5,8-diazadodeca-3,9-diene-2,11-dione) were prepared in good yield from the readily available [Ti(NBut)Cl2(py)3] and the dilithium or disodium salts of the tetradentate ligands. The Ti=NBut groups in 2 and 3 underwent imido group exchange reactions with anilines to form [Ti(NR)(Mentaa)] (n = 4, R = C6H3Me2-2,6 4, Ph, C6H4(NO2)-4, C6H4(NMe2)-4; n = 4 or 8, R = C6H4Me-4), and with H2E (E = O or S) to give the oxo and sulfido analogues [Ti(E)(Me4taa)]. Compound 4 was also prepared in good yield from [Ti(NC6H3Me2-2,6)Cl2(py) 3] and Li2[Me4taa]. Reaction of 2 with 2 or 1 equivalents of ROH (R = Me or C6H3Me2-2,6) or pinacol afforded [Ti(OR)2(Me4taa)] and [Ti{OC(Me)2C(Me)2O}(Me4taa)] respectively. The crystal structures of 3 and 4 have been described. |
| first_indexed | 2024-03-06T23:40:14Z |
| format | Journal article |
| id | oxford-uuid:6f0c6644-fdce-499e-a5a9-1a1bbe22d551 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T23:40:14Z |
| publishDate | 1998 |
| record_format | dspace |
| spelling | oxford-uuid:6f0c6644-fdce-499e-a5a9-1a1bbe22d5512022-03-26T19:28:20ZTitanium imido complexes with tetraaza macrocyclic ligandsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:6f0c6644-fdce-499e-a5a9-1a1bbe22d551EnglishSymplectic Elements at Oxford1998Swallow, DMcInnes, JMountford, PTetraaza macrocycle-supported tert-bulyl titanium imido complexes [Ti(NBut)(Mentaa)] (n = 4 2 or 8 3; H2Mentaa = 6,8,15,17-tetra- or 2,3,6,8,11,12,17,18-octa-methyl-5,14-dihydrodibenzo[b,i][1,4,8,11] tetraazacyclotetradecine, respectively), [Ti(NBut)(Me4taen)] (5, H2Me4taen = 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraene) and [Ti(NBut)(TTP)] (6, H2TTP = 5,10,15,20-tetratolylporphyrin) together with the N2O2-donor Schiff base analogue [Ti(NBut)(acen)] (7, H2acen = 4,9-dimethyl-5,8-diazadodeca-3,9-diene-2,11-dione) were prepared in good yield from the readily available [Ti(NBut)Cl2(py)3] and the dilithium or disodium salts of the tetradentate ligands. The Ti=NBut groups in 2 and 3 underwent imido group exchange reactions with anilines to form [Ti(NR)(Mentaa)] (n = 4, R = C6H3Me2-2,6 4, Ph, C6H4(NO2)-4, C6H4(NMe2)-4; n = 4 or 8, R = C6H4Me-4), and with H2E (E = O or S) to give the oxo and sulfido analogues [Ti(E)(Me4taa)]. Compound 4 was also prepared in good yield from [Ti(NC6H3Me2-2,6)Cl2(py) 3] and Li2[Me4taa]. Reaction of 2 with 2 or 1 equivalents of ROH (R = Me or C6H3Me2-2,6) or pinacol afforded [Ti(OR)2(Me4taa)] and [Ti{OC(Me)2C(Me)2O}(Me4taa)] respectively. The crystal structures of 3 and 4 have been described. |
| spellingShingle | Swallow, D McInnes, J Mountford, P Titanium imido complexes with tetraaza macrocyclic ligands |
| title | Titanium imido complexes with tetraaza macrocyclic ligands |
| title_full | Titanium imido complexes with tetraaza macrocyclic ligands |
| title_fullStr | Titanium imido complexes with tetraaza macrocyclic ligands |
| title_full_unstemmed | Titanium imido complexes with tetraaza macrocyclic ligands |
| title_short | Titanium imido complexes with tetraaza macrocyclic ligands |
| title_sort | titanium imido complexes with tetraaza macrocyclic ligands |
| work_keys_str_mv | AT swallowd titaniumimidocomplexeswithtetraazamacrocyclicligands AT mcinnesj titaniumimidocomplexeswithtetraazamacrocyclicligands AT mountfordp titaniumimidocomplexeswithtetraazamacrocyclicligands |