Rh(I)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine): Synthesis, Characterization, and Application as an Initiator in the Stereoregular (Co)Polymerization of Phenylacetylenes
The synthesis of the Rh(I)-aryl complex, Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) is reported and its efficacy as an initiator for the (co)polymerization of phenylacetylenes established. The X-ray crystal structure indicates that the complex adopts a slightly distorted square planar geometry whose purity and s...
| Main Authors: | , , , , , , |
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| Format: | Journal Article |
| Language: | English |
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AMER CHEMICAL SOC
2020
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| Subjects: | |
| Online Access: | http://hdl.handle.net/20.500.11937/77877 |
| _version_ | 1848763910312689664 |
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| author | Loong Tan, N.S. Nealon, G.L. Turner, G.F. Moggach, S.A. Ogden, Mark Massi, Max Lowe, Andrew |
| author_facet | Loong Tan, N.S. Nealon, G.L. Turner, G.F. Moggach, S.A. Ogden, Mark Massi, Max Lowe, Andrew |
| author_sort | Loong Tan, N.S. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | The synthesis of the Rh(I)-aryl complex, Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) is reported and its efficacy as an initiator for the (co)polymerization of phenylacetylenes established. The X-ray crystal structure indicates that the complex adopts a slightly distorted square planar geometry whose purity and structure was also confirmed by elemental analysis and 1H, 13C, 31P, 19F, 103Rh, and 31P-103Rh{1H} HMQC NMR spectroscopy. We demonstrate that Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) mediates the (co)polymerization of phenylacetylenes in a controlled fashion with initiation efficiencies as high as 0.98, as evidenced by the pseudo-first-order kinetic and number-average molecular weight versus conversion profiles. The ability to form well-defined AB diblock copolymers, in a stereoregular manner, by sequential monomer addition is verified in the block copolymerization of phenylacetylene with 4-fluorophenylacetylene with quantitative crossover efficiency, as determined by size exclusion chromatography. |
| first_indexed | 2025-11-14T11:10:58Z |
| format | Journal Article |
| id | curtin-20.500.11937-77877 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T11:10:58Z |
| publishDate | 2020 |
| publisher | AMER CHEMICAL SOC |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-778772020-04-28T01:57:36Z Rh(I)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine): Synthesis, Characterization, and Application as an Initiator in the Stereoregular (Co)Polymerization of Phenylacetylenes Loong Tan, N.S. Nealon, G.L. Turner, G.F. Moggach, S.A. Ogden, Mark Massi, Max Lowe, Andrew Science & Technology Physical Sciences Polymer Science LIVING POLYMERIZATION RHODIUM CATALYSTS BLOCK-COPOLYMERS MOLECULAR-WEIGHT COMPLEXES LIGAND The synthesis of the Rh(I)-aryl complex, Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) is reported and its efficacy as an initiator for the (co)polymerization of phenylacetylenes established. The X-ray crystal structure indicates that the complex adopts a slightly distorted square planar geometry whose purity and structure was also confirmed by elemental analysis and 1H, 13C, 31P, 19F, 103Rh, and 31P-103Rh{1H} HMQC NMR spectroscopy. We demonstrate that Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) mediates the (co)polymerization of phenylacetylenes in a controlled fashion with initiation efficiencies as high as 0.98, as evidenced by the pseudo-first-order kinetic and number-average molecular weight versus conversion profiles. The ability to form well-defined AB diblock copolymers, in a stereoregular manner, by sequential monomer addition is verified in the block copolymerization of phenylacetylene with 4-fluorophenylacetylene with quantitative crossover efficiency, as determined by size exclusion chromatography. 2020 Journal Article http://hdl.handle.net/20.500.11937/77877 10.1021/acsmacrolett.9b00975 English AMER CHEMICAL SOC restricted |
| spellingShingle | Science & Technology Physical Sciences Polymer Science LIVING POLYMERIZATION RHODIUM CATALYSTS BLOCK-COPOLYMERS MOLECULAR-WEIGHT COMPLEXES LIGAND Loong Tan, N.S. Nealon, G.L. Turner, G.F. Moggach, S.A. Ogden, Mark Massi, Max Lowe, Andrew Rh(I)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine): Synthesis, Characterization, and Application as an Initiator in the Stereoregular (Co)Polymerization of Phenylacetylenes |
| title | Rh(I)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine): Synthesis, Characterization, and Application as an Initiator in the Stereoregular (Co)Polymerization of Phenylacetylenes |
| title_full | Rh(I)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine): Synthesis, Characterization, and Application as an Initiator in the Stereoregular (Co)Polymerization of Phenylacetylenes |
| title_fullStr | Rh(I)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine): Synthesis, Characterization, and Application as an Initiator in the Stereoregular (Co)Polymerization of Phenylacetylenes |
| title_full_unstemmed | Rh(I)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine): Synthesis, Characterization, and Application as an Initiator in the Stereoregular (Co)Polymerization of Phenylacetylenes |
| title_short | Rh(I)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine): Synthesis, Characterization, and Application as an Initiator in the Stereoregular (Co)Polymerization of Phenylacetylenes |
| title_sort | rh(i)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine): synthesis, characterization, and application as an initiator in the stereoregular (co)polymerization of phenylacetylenes |
| topic | Science & Technology Physical Sciences Polymer Science LIVING POLYMERIZATION RHODIUM CATALYSTS BLOCK-COPOLYMERS MOLECULAR-WEIGHT COMPLEXES LIGAND |
| url | http://hdl.handle.net/20.500.11937/77877 |