Influence of ligand backbone flexibility in group 4 metal complexes of tetradentate mixed tertiary amine/alkoxide ligands
Simple epoxide ring opening chemistry using the cyclic secondary amine 1,4-diazacycloheptane or the related linear species N,N′- dimethylethylenediamine, and racemic (±)-3,3-dimethyl-1,2-epoxybutane gives access to the pendant alcohol functionalised ditertiary amine pro-ligands [HOCH(tBu)CH2N(R)CH2]...
| Main Authors: | , , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
2007
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| _version_ | 1797094123208966144 |
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| author | Day, J Baghurst, R Strevens, R Light, M Hursthouse, M Stengel, B Fallis, I Aldridge, S |
| author_facet | Day, J Baghurst, R Strevens, R Light, M Hursthouse, M Stengel, B Fallis, I Aldridge, S |
| author_sort | Day, J |
| collection | OXFORD |
| description | Simple epoxide ring opening chemistry using the cyclic secondary amine 1,4-diazacycloheptane or the related linear species N,N′- dimethylethylenediamine, and racemic (±)-3,3-dimethyl-1,2-epoxybutane gives access to the pendant alcohol functionalised ditertiary amine pro-ligands [HOCH(tBu)CH2N(R)CH2]2 (H 2L1: R2 = CH2CH2CH 2; H2L2: R2 = Me2). The contrasting reactions of H2L1 and H2L 2 towards homoleptic group 4 alkoxides highlight the crucial role of ligand backbone flexibility in complex formation. Thus, the chemistry of the more conformationally rigid system (L1)2- appears to be constrained by the cyclic ligand core, such that it adopts a bridging (μ2:η2,η2) mode of coordination towards Ti(iv), leading to dinuclear metal systems [e.g. L1Ti 2(OiPr)6]. By contrast, the more flexible linear system (L2)2- binds to both Ti(iv) and Zr(iv) in a chelating fashion leading, for example, to the synthesis of the C2 symmetric mononuclear complex rac-L2Ti(OiPr)2. Thus, a simple synthesis of diastereomerically pure, C2 symmetric, geometrically cis octahedral Ti(iv) complexes from racemic precursors is presented. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. |
| first_indexed | 2024-03-07T04:09:46Z |
| format | Journal article |
| id | oxford-uuid:c77087cc-cd62-4804-8a05-486e0aa37ba1 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T04:09:46Z |
| publishDate | 2007 |
| record_format | dspace |
| spelling | oxford-uuid:c77087cc-cd62-4804-8a05-486e0aa37ba12022-03-27T06:45:02ZInfluence of ligand backbone flexibility in group 4 metal complexes of tetradentate mixed tertiary amine/alkoxide ligandsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:c77087cc-cd62-4804-8a05-486e0aa37ba1EnglishSymplectic Elements at Oxford2007Day, JBaghurst, RStrevens, RLight, MHursthouse, MStengel, BFallis, IAldridge, SSimple epoxide ring opening chemistry using the cyclic secondary amine 1,4-diazacycloheptane or the related linear species N,N′- dimethylethylenediamine, and racemic (±)-3,3-dimethyl-1,2-epoxybutane gives access to the pendant alcohol functionalised ditertiary amine pro-ligands [HOCH(tBu)CH2N(R)CH2]2 (H 2L1: R2 = CH2CH2CH 2; H2L2: R2 = Me2). The contrasting reactions of H2L1 and H2L 2 towards homoleptic group 4 alkoxides highlight the crucial role of ligand backbone flexibility in complex formation. Thus, the chemistry of the more conformationally rigid system (L1)2- appears to be constrained by the cyclic ligand core, such that it adopts a bridging (μ2:η2,η2) mode of coordination towards Ti(iv), leading to dinuclear metal systems [e.g. L1Ti 2(OiPr)6]. By contrast, the more flexible linear system (L2)2- binds to both Ti(iv) and Zr(iv) in a chelating fashion leading, for example, to the synthesis of the C2 symmetric mononuclear complex rac-L2Ti(OiPr)2. Thus, a simple synthesis of diastereomerically pure, C2 symmetric, geometrically cis octahedral Ti(iv) complexes from racemic precursors is presented. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. |
| spellingShingle | Day, J Baghurst, R Strevens, R Light, M Hursthouse, M Stengel, B Fallis, I Aldridge, S Influence of ligand backbone flexibility in group 4 metal complexes of tetradentate mixed tertiary amine/alkoxide ligands |
| title | Influence of ligand backbone flexibility in group 4 metal complexes of tetradentate mixed tertiary amine/alkoxide ligands |
| title_full | Influence of ligand backbone flexibility in group 4 metal complexes of tetradentate mixed tertiary amine/alkoxide ligands |
| title_fullStr | Influence of ligand backbone flexibility in group 4 metal complexes of tetradentate mixed tertiary amine/alkoxide ligands |
| title_full_unstemmed | Influence of ligand backbone flexibility in group 4 metal complexes of tetradentate mixed tertiary amine/alkoxide ligands |
| title_short | Influence of ligand backbone flexibility in group 4 metal complexes of tetradentate mixed tertiary amine/alkoxide ligands |
| title_sort | influence of ligand backbone flexibility in group 4 metal complexes of tetradentate mixed tertiary amine alkoxide ligands |
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