Synthesis and ethylene polymerization capability of metallocene-like imido titanium dialkyl compounds and their reactions with (AlBu3)-Bu-i
A series of alkyl- and aryl-imido titanium dialkyl compounds Ti(N'Bu)(Me3[9]aneN3)R2 (R = Me (1), CH 2SiMe3 (3), CH2tBu (4), CH 2Ph (5)), Ti(NR)(Me3[9]aneN3)Me2 (R = iPr (6), Ph. (7), 3,5-C6H3(CF 3)2 (8), 2,6-C6H3iPr 2 (9), 2-C6H4CF3 (10), 2-C 6H4tBu (11)), and Ti(NR)(Me3[9] aneN3)(CH2SiMe3)2 (...
| Main Authors: | , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
2006
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| _version_ | 1797098854564233216 |
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| author | Bolton, P Adams, N Clot, E Cowley, A Wilson, P Schroeder, M Mountford, P |
| author_facet | Bolton, P Adams, N Clot, E Cowley, A Wilson, P Schroeder, M Mountford, P |
| author_sort | Bolton, P |
| collection | OXFORD |
| description | A series of alkyl- and aryl-imido titanium dialkyl compounds Ti(N'Bu)(Me3[9]aneN3)R2 (R = Me (1), CH 2SiMe3 (3), CH2tBu (4), CH 2Ph (5)), Ti(NR)(Me3[9]aneN3)Me2 (R = iPr (6), Ph. (7), 3,5-C6H3(CF 3)2 (8), 2,6-C6H3iPr 2 (9), 2-C6H4CF3 (10), 2-C 6H4tBu (11)), and Ti(NR)(Me3[9] aneN3)(CH2SiMe3)2 (R = iPr (12), ArF (13)) were prepared and crystallographically characterized in the case of 1, 6-9, and 11 (Me3-[9]aneN3 = 1,4,7-trimethyl triazacyclononane; ArF = C6F 5). These compounds, isolobal with the titanocenes Cp 2TiR2, were thermally stable at elevated temperatures except for 4. Reaction of 7 with [Ph3C][BArF4] (TB) and diisopropylcarbodiimide in CH2Cl2 gave the Ti-Me insertion product [Ti(NPh)(Me3[9]-aneN3){MeC(N iPr)2}][BArF4] (15-BArF4). The corresponding reaction of 7 in the absence of organic substrate gave [Ti2(μ-NPh)2(Me3[9]aneN 3)2Cl2][BArF4] 2 via a solvent activation reaction. The roomtemperature ethylene polymerization capabilities of the dialkyl compounds were evaluated using TB cocatalyst in the presence of AliBu3 (TIBA). Among the dimethyl precatalysts, only the systems 1 and 11, with the bulkiest imido groups, showed high productivities (6230 and 1210 kg mol-1 h -1 bar-1, respectively). The productivites of the other ferf-butyl imido precatalysts 3 and 4 (130 and 120 kg mol-1 h -1 bar-1, respectively) were substantially lower than that of 1. The catalyst system 1/TIBA (2500 equiv, no added TB) was also active for ethylene polymerization (225 kg mol-1 h-1 bar -1). The less productive imido dialkyl precatalysts all formed complex mixtures on exposure to TIBA. The polyethylenes produced with 1, 3, and 5-11 generally had Mw/Mn values in the range 2.6-3.0. The PE formed with 1/TB/TIBA was terminated only by methyl end groups, consistent with chain transfer to TIBA followed by subsequent β-H transfer by the resultant titanium isobutyl cation. The alkyl cations [Ti(NtBu) (Me3[9]aneN3)R]+ (R = Me or CH 2SiMe3) reacted rapidly with TIBA in C6D 5Br at -30°C, forming isobutene. DFT calculations found that TIBA adducts of the model methyl cation [Ti(NMe)(H3[9]aneN 3)Me]+ were energetically favorable by ca. -80 to -110 kJ mol-1. Whereas 1 alone or with AlMe3 present has been shown to form only Ph3CMe on reaction with [Ph3C]+, 1:1 mixtures of 1 and TIBA gave Ph3CH as the only tritylcontaining product, suggesting a key role for transient [AliBu2] + in the activation process for these catalysts. Overall, the imido group in the Ti(NR)(Me3[9]aneN3)Me2/TB/TIBA catalysts systems appears to have two roles: to stabilize the dialkyl precatalyst toward degradation by the TIBA itself prior to activation, and to inhibit the formation of catalytically inactive hetero- or homo-bimetallic complexes. © 2006 American Chemical Society. |
| first_indexed | 2024-03-07T05:15:38Z |
| format | Journal article |
| id | oxford-uuid:dd171860-630b-47bd-83d2-4410e5e2c10a |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T05:15:38Z |
| publishDate | 2006 |
| record_format | dspace |
| spelling | oxford-uuid:dd171860-630b-47bd-83d2-4410e5e2c10a2022-03-27T09:22:29ZSynthesis and ethylene polymerization capability of metallocene-like imido titanium dialkyl compounds and their reactions with (AlBu3)-Bu-iJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:dd171860-630b-47bd-83d2-4410e5e2c10aEnglishSymplectic Elements at Oxford2006Bolton, PAdams, NClot, ECowley, AWilson, PSchroeder, MMountford, PA series of alkyl- and aryl-imido titanium dialkyl compounds Ti(N'Bu)(Me3[9]aneN3)R2 (R = Me (1), CH 2SiMe3 (3), CH2tBu (4), CH 2Ph (5)), Ti(NR)(Me3[9]aneN3)Me2 (R = iPr (6), Ph. (7), 3,5-C6H3(CF 3)2 (8), 2,6-C6H3iPr 2 (9), 2-C6H4CF3 (10), 2-C 6H4tBu (11)), and Ti(NR)(Me3[9] aneN3)(CH2SiMe3)2 (R = iPr (12), ArF (13)) were prepared and crystallographically characterized in the case of 1, 6-9, and 11 (Me3-[9]aneN3 = 1,4,7-trimethyl triazacyclononane; ArF = C6F 5). These compounds, isolobal with the titanocenes Cp 2TiR2, were thermally stable at elevated temperatures except for 4. Reaction of 7 with [Ph3C][BArF4] (TB) and diisopropylcarbodiimide in CH2Cl2 gave the Ti-Me insertion product [Ti(NPh)(Me3[9]-aneN3){MeC(N iPr)2}][BArF4] (15-BArF4). The corresponding reaction of 7 in the absence of organic substrate gave [Ti2(μ-NPh)2(Me3[9]aneN 3)2Cl2][BArF4] 2 via a solvent activation reaction. The roomtemperature ethylene polymerization capabilities of the dialkyl compounds were evaluated using TB cocatalyst in the presence of AliBu3 (TIBA). Among the dimethyl precatalysts, only the systems 1 and 11, with the bulkiest imido groups, showed high productivities (6230 and 1210 kg mol-1 h -1 bar-1, respectively). The productivites of the other ferf-butyl imido precatalysts 3 and 4 (130 and 120 kg mol-1 h -1 bar-1, respectively) were substantially lower than that of 1. The catalyst system 1/TIBA (2500 equiv, no added TB) was also active for ethylene polymerization (225 kg mol-1 h-1 bar -1). The less productive imido dialkyl precatalysts all formed complex mixtures on exposure to TIBA. The polyethylenes produced with 1, 3, and 5-11 generally had Mw/Mn values in the range 2.6-3.0. The PE formed with 1/TB/TIBA was terminated only by methyl end groups, consistent with chain transfer to TIBA followed by subsequent β-H transfer by the resultant titanium isobutyl cation. The alkyl cations [Ti(NtBu) (Me3[9]aneN3)R]+ (R = Me or CH 2SiMe3) reacted rapidly with TIBA in C6D 5Br at -30°C, forming isobutene. DFT calculations found that TIBA adducts of the model methyl cation [Ti(NMe)(H3[9]aneN 3)Me]+ were energetically favorable by ca. -80 to -110 kJ mol-1. Whereas 1 alone or with AlMe3 present has been shown to form only Ph3CMe on reaction with [Ph3C]+, 1:1 mixtures of 1 and TIBA gave Ph3CH as the only tritylcontaining product, suggesting a key role for transient [AliBu2] + in the activation process for these catalysts. Overall, the imido group in the Ti(NR)(Me3[9]aneN3)Me2/TB/TIBA catalysts systems appears to have two roles: to stabilize the dialkyl precatalyst toward degradation by the TIBA itself prior to activation, and to inhibit the formation of catalytically inactive hetero- or homo-bimetallic complexes. © 2006 American Chemical Society. |
| spellingShingle | Bolton, P Adams, N Clot, E Cowley, A Wilson, P Schroeder, M Mountford, P Synthesis and ethylene polymerization capability of metallocene-like imido titanium dialkyl compounds and their reactions with (AlBu3)-Bu-i |
| title | Synthesis and ethylene polymerization capability of metallocene-like imido titanium dialkyl compounds and their reactions with (AlBu3)-Bu-i |
| title_full | Synthesis and ethylene polymerization capability of metallocene-like imido titanium dialkyl compounds and their reactions with (AlBu3)-Bu-i |
| title_fullStr | Synthesis and ethylene polymerization capability of metallocene-like imido titanium dialkyl compounds and their reactions with (AlBu3)-Bu-i |
| title_full_unstemmed | Synthesis and ethylene polymerization capability of metallocene-like imido titanium dialkyl compounds and their reactions with (AlBu3)-Bu-i |
| title_short | Synthesis and ethylene polymerization capability of metallocene-like imido titanium dialkyl compounds and their reactions with (AlBu3)-Bu-i |
| title_sort | synthesis and ethylene polymerization capability of metallocene like imido titanium dialkyl compounds and their reactions with albu3 bu i |
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