New diamide-diamine ligands and their zirconium and hafnium dichloride and bis(dimethylamide) complexes.
The multigram syntheses of the protio ligands (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NHSiMe(2)R)(2) (R = Me, H(2)N(2)NN' 3; R = (t)Bu, H(2)N(2)NN() 4) are described via reactions of the previously reported (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NH(2))(2) (1). A new synthesis of 1 is reported starting from 2-amin...
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| Format: | Journal article |
| Language: | English |
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2002
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| _version_ | 1797106251657641984 |
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| author | Skinner, M Li, Y Mountford, P |
| author_facet | Skinner, M Li, Y Mountford, P |
| author_sort | Skinner, M |
| collection | OXFORD |
| description | The multigram syntheses of the protio ligands (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NHSiMe(2)R)(2) (R = Me, H(2)N(2)NN' 3; R = (t)Bu, H(2)N(2)NN() 4) are described via reactions of the previously reported (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NH(2))(2) (1). A new synthesis of 1 is reported starting from 2-aminomethylpyridine and N-tosylaziridine, proceeding via (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NHTs)(2) (2). Reaction of H(2)N(2)NN' or H(2)N(2)NN* with (n)BuLi gives good yields of the dilithiated derivatives Li(2)N(2)NN' and Li(2)N(2)NN*. Reaction of H(2)N(2)NN' or H(2)N(2)NN* with [MCl(2)(CH(2)SiMe(3))(2)(Et(2)O)(2)] gives the cis-dichloride complexes [MCl(2)(L)] (L = N(2)NN', M = Zr 7 or Hf 8; L = N(2)NN(), M = Zr 9). The corresponding reactions of H(2)N(2)NN' or H(2)N(2)NN* with [Zr(NMe(2))(4)] afford the bis(dimethylamide) derivatives [Zr(NMe(2))(2)(L)] (L = N(2)NN' 10 or N(2)NN* 11). All of these protonolysis reactions proceed smoothly and in good yields. Attempts to prepare the titanium complexes [Ti(X)(2)(N(2)NN')] (X = Cl or NMe(2)) were unsuccessful. The X-ray crystal structures of (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NHTs)(2).EtOH, [ZrCl(2)(N(2)NN')].0.5C(6)H(6), [Zr(NMe(2))(2)(N(2)NN')], and [Zr(NMe(2))(2)(N(2)NN*)] are reported. |
| first_indexed | 2024-03-07T06:59:04Z |
| format | Journal article |
| id | oxford-uuid:ff1ce3fa-530d-4069-b6dd-c60a4ecba8ff |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T06:59:04Z |
| publishDate | 2002 |
| record_format | dspace |
| spelling | oxford-uuid:ff1ce3fa-530d-4069-b6dd-c60a4ecba8ff2022-03-27T13:42:04ZNew diamide-diamine ligands and their zirconium and hafnium dichloride and bis(dimethylamide) complexes.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:ff1ce3fa-530d-4069-b6dd-c60a4ecba8ffEnglishSymplectic Elements at Oxford2002Skinner, MLi, YMountford, PThe multigram syntheses of the protio ligands (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NHSiMe(2)R)(2) (R = Me, H(2)N(2)NN' 3; R = (t)Bu, H(2)N(2)NN() 4) are described via reactions of the previously reported (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NH(2))(2) (1). A new synthesis of 1 is reported starting from 2-aminomethylpyridine and N-tosylaziridine, proceeding via (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NHTs)(2) (2). Reaction of H(2)N(2)NN' or H(2)N(2)NN* with (n)BuLi gives good yields of the dilithiated derivatives Li(2)N(2)NN' and Li(2)N(2)NN*. Reaction of H(2)N(2)NN' or H(2)N(2)NN* with [MCl(2)(CH(2)SiMe(3))(2)(Et(2)O)(2)] gives the cis-dichloride complexes [MCl(2)(L)] (L = N(2)NN', M = Zr 7 or Hf 8; L = N(2)NN(), M = Zr 9). The corresponding reactions of H(2)N(2)NN' or H(2)N(2)NN* with [Zr(NMe(2))(4)] afford the bis(dimethylamide) derivatives [Zr(NMe(2))(2)(L)] (L = N(2)NN' 10 or N(2)NN* 11). All of these protonolysis reactions proceed smoothly and in good yields. Attempts to prepare the titanium complexes [Ti(X)(2)(N(2)NN')] (X = Cl or NMe(2)) were unsuccessful. The X-ray crystal structures of (2-NC(5)H(4))CH(2)N(CH(2)CH(2)NHTs)(2).EtOH, [ZrCl(2)(N(2)NN')].0.5C(6)H(6), [Zr(NMe(2))(2)(N(2)NN')], and [Zr(NMe(2))(2)(N(2)NN*)] are reported. |
| spellingShingle | Skinner, M Li, Y Mountford, P New diamide-diamine ligands and their zirconium and hafnium dichloride and bis(dimethylamide) complexes. |
| title | New diamide-diamine ligands and their zirconium and hafnium dichloride and bis(dimethylamide) complexes. |
| title_full | New diamide-diamine ligands and their zirconium and hafnium dichloride and bis(dimethylamide) complexes. |
| title_fullStr | New diamide-diamine ligands and their zirconium and hafnium dichloride and bis(dimethylamide) complexes. |
| title_full_unstemmed | New diamide-diamine ligands and their zirconium and hafnium dichloride and bis(dimethylamide) complexes. |
| title_short | New diamide-diamine ligands and their zirconium and hafnium dichloride and bis(dimethylamide) complexes. |
| title_sort | new diamide diamine ligands and their zirconium and hafnium dichloride and bis dimethylamide complexes |
| work_keys_str_mv | AT skinnerm newdiamidediamineligandsandtheirzirconiumandhafniumdichlorideandbisdimethylamidecomplexes AT liy newdiamidediamineligandsandtheirzirconiumandhafniumdichlorideandbisdimethylamidecomplexes AT mountfordp newdiamidediamineligandsandtheirzirconiumandhafniumdichlorideandbisdimethylamidecomplexes |