Sulfonamide-supported group 4 catalysts for the ring-opening polymerization of epsilon-caprolactone and rac-lactide.
Reaction of RCH(2)N(CH(2)CH(2)NHSO(2)Tol)(2) (R = 2-NC(5)H(4) (8, H(2)L(py)) or MeOCH(2) (9, H(2)L(OMe))) with Ti(NMe(2))(4) at room temperature afforded Ti(L(py))(NMe(2))(2) (10) or Ti(L(OMe))(NMe(2))(2) (11), respectively, which contain tetradentate bis(sulfonamide)amine ligands. The corresponding...
| Glavni autori: | , , |
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| Format: | Journal article |
| Jezik: | English |
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2009
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| _version_ | 1826281198189543424 |
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| author | Schwarz, A Thompson, A Mountford, P |
| author_facet | Schwarz, A Thompson, A Mountford, P |
| author_sort | Schwarz, A |
| collection | OXFORD |
| description | Reaction of RCH(2)N(CH(2)CH(2)NHSO(2)Tol)(2) (R = 2-NC(5)H(4) (8, H(2)L(py)) or MeOCH(2) (9, H(2)L(OMe))) with Ti(NMe(2))(4) at room temperature afforded Ti(L(py))(NMe(2))(2) (10) or Ti(L(OMe))(NMe(2))(2) (11), respectively, which contain tetradentate bis(sulfonamide)amine ligands. The corresponding reactions with Ti(O(i)Pr)(4) or Zr(O(i)Pr)(4) x HO(i)Pr required more forcing conditions to form the homologous bis(isopropoxide) analogues, M(L(R))(O(i)Pr)(2) (M = Ti, R = py (12) or OMe (14); M = Zr, R = py (13) or OMe (15)). Reaction of Ti(NMe(2))(2)(O(i)Pr)(2) with H(2)L(R) formed 12 or 14 under milder conditions. The X-ray structures of 10-15 have been determined revealing C(s) symmetric, 6-coordinate complexes except for 13 which is 7-coordinate with one kappa(2)(N,O) bound sulfonamide donor. Compounds 10-15 are all catalysts for the ring-opening polymerization (ROP) of epsilon-caprolactone, with the isopropoxide compounds being the fastest and best controlled, especially in the case of zirconium. In addition, Zr(L(OMe))(O(i)Pr) (2) (15) was an efficient catalyst for the well-controlled ROP of rac-lactide both in toluene at 100 degrees C and in the melt at 130 degrees C, giving atactic poly(rac-lactide). The polymerization rates and control achieved for 13 and 15 are comparable to those of the well-established bis(phenolate)amine-supported Group 4 systems reported recently. |
| first_indexed | 2024-03-07T00:25:12Z |
| format | Journal article |
| id | oxford-uuid:7de95b11-6e8b-44ba-948e-bd8374c8f1bb |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T00:25:12Z |
| publishDate | 2009 |
| record_format | dspace |
| spelling | oxford-uuid:7de95b11-6e8b-44ba-948e-bd8374c8f1bb2022-03-26T21:06:44ZSulfonamide-supported group 4 catalysts for the ring-opening polymerization of epsilon-caprolactone and rac-lactide.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:7de95b11-6e8b-44ba-948e-bd8374c8f1bbEnglishSymplectic Elements at Oxford2009Schwarz, AThompson, AMountford, PReaction of RCH(2)N(CH(2)CH(2)NHSO(2)Tol)(2) (R = 2-NC(5)H(4) (8, H(2)L(py)) or MeOCH(2) (9, H(2)L(OMe))) with Ti(NMe(2))(4) at room temperature afforded Ti(L(py))(NMe(2))(2) (10) or Ti(L(OMe))(NMe(2))(2) (11), respectively, which contain tetradentate bis(sulfonamide)amine ligands. The corresponding reactions with Ti(O(i)Pr)(4) or Zr(O(i)Pr)(4) x HO(i)Pr required more forcing conditions to form the homologous bis(isopropoxide) analogues, M(L(R))(O(i)Pr)(2) (M = Ti, R = py (12) or OMe (14); M = Zr, R = py (13) or OMe (15)). Reaction of Ti(NMe(2))(2)(O(i)Pr)(2) with H(2)L(R) formed 12 or 14 under milder conditions. The X-ray structures of 10-15 have been determined revealing C(s) symmetric, 6-coordinate complexes except for 13 which is 7-coordinate with one kappa(2)(N,O) bound sulfonamide donor. Compounds 10-15 are all catalysts for the ring-opening polymerization (ROP) of epsilon-caprolactone, with the isopropoxide compounds being the fastest and best controlled, especially in the case of zirconium. In addition, Zr(L(OMe))(O(i)Pr) (2) (15) was an efficient catalyst for the well-controlled ROP of rac-lactide both in toluene at 100 degrees C and in the melt at 130 degrees C, giving atactic poly(rac-lactide). The polymerization rates and control achieved for 13 and 15 are comparable to those of the well-established bis(phenolate)amine-supported Group 4 systems reported recently. |
| spellingShingle | Schwarz, A Thompson, A Mountford, P Sulfonamide-supported group 4 catalysts for the ring-opening polymerization of epsilon-caprolactone and rac-lactide. |
| title | Sulfonamide-supported group 4 catalysts for the ring-opening polymerization of epsilon-caprolactone and rac-lactide. |
| title_full | Sulfonamide-supported group 4 catalysts for the ring-opening polymerization of epsilon-caprolactone and rac-lactide. |
| title_fullStr | Sulfonamide-supported group 4 catalysts for the ring-opening polymerization of epsilon-caprolactone and rac-lactide. |
| title_full_unstemmed | Sulfonamide-supported group 4 catalysts for the ring-opening polymerization of epsilon-caprolactone and rac-lactide. |
| title_short | Sulfonamide-supported group 4 catalysts for the ring-opening polymerization of epsilon-caprolactone and rac-lactide. |
| title_sort | sulfonamide supported group 4 catalysts for the ring opening polymerization of epsilon caprolactone and rac lactide |
| work_keys_str_mv | AT schwarza sulfonamidesupportedgroup4catalystsfortheringopeningpolymerizationofepsiloncaprolactoneandraclactide AT thompsona sulfonamidesupportedgroup4catalystsfortheringopeningpolymerizationofepsiloncaprolactoneandraclactide AT mountfordp sulfonamidesupportedgroup4catalystsfortheringopeningpolymerizationofepsiloncaprolactoneandraclactide |