Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands
Imido alkylidene complexes of Mo and W and oxo alkylidene complexes of W that contain thiophenoxide ligands of the type S-2,3,5,6-Ph[subscript 4]C[subscript 6]H (STPP) and S-2,6-(mesityl)[subscript 2]C[subscript 6]H[subscript 3] (SHMT = S-hexamethylterphenyl) have been prepared in order to compare t...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2017
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| Online Access: | http://hdl.handle.net/1721.1/109366 https://orcid.org/0000-0001-5827-3552 |
| _version_ | 1811093741451083776 |
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| author | Hoveyda, Amir H. Townsend, Erik M. Hyvl, Jakub Forrest Jr, William P Schrock, Richard Royce Mueller, Peter |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Hoveyda, Amir H. Townsend, Erik M. Hyvl, Jakub Forrest Jr, William P Schrock, Richard Royce Mueller, Peter |
| author_sort | Hoveyda, Amir H. |
| collection | MIT |
| description | Imido alkylidene complexes of Mo and W and oxo alkylidene complexes of W that contain thiophenoxide ligands of the type S-2,3,5,6-Ph[subscript 4]C[subscript 6]H (STPP) and S-2,6-(mesityl)[subscript 2]C[subscript 6]H[subscript 3] (SHMT = S-hexamethylterphenyl) have been prepared in order to compare their metathesis activity with that of the analogous phenoxide complexes. All thiolate complexes were significantly slower (up to ∼10× slower) for the metathesis homocoupling of 1-octene or polymerization of 2,3-dicarbomethoxynorbornene, and none of them was Z-selective. The slower rates could be attributed to the greater σ-donating ability of a thiophenoxide versus the analogous phenoxide and consequently a higher electron density at the metal in the thiophenoxide complexes. |
| first_indexed | 2024-09-23T15:49:54Z |
| format | Article |
| id | mit-1721.1/109366 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T15:49:54Z |
| publishDate | 2017 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1093662022-10-02T04:25:45Z Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands Hoveyda, Amir H. Townsend, Erik M. Hyvl, Jakub Forrest Jr, William P Schrock, Richard Royce Mueller, Peter Massachusetts Institute of Technology. Department of Chemistry Townsend, Erik M. Hyvl, Jakub Forrest Jr, William P Schrock, Richard Royce Mueller, Peter Imido alkylidene complexes of Mo and W and oxo alkylidene complexes of W that contain thiophenoxide ligands of the type S-2,3,5,6-Ph[subscript 4]C[subscript 6]H (STPP) and S-2,6-(mesityl)[subscript 2]C[subscript 6]H[subscript 3] (SHMT = S-hexamethylterphenyl) have been prepared in order to compare their metathesis activity with that of the analogous phenoxide complexes. All thiolate complexes were significantly slower (up to ∼10× slower) for the metathesis homocoupling of 1-octene or polymerization of 2,3-dicarbomethoxynorbornene, and none of them was Z-selective. The slower rates could be attributed to the greater σ-donating ability of a thiophenoxide versus the analogous phenoxide and consequently a higher electron density at the metal in the thiophenoxide complexes. National Institutes of Health (U.S.) (Grant GM-59426) 2017-05-26T14:08:20Z 2017-05-26T14:08:20Z 2014-09 2014-06 Article http://purl.org/eprint/type/JournalArticle 0276-7333 1520-6041 http://hdl.handle.net/1721.1/109366 Townsend, Erik M. et al. “Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands.” Organometallics 33.19 (2014): 5334–5341. © 2014 American Chemical Society 5 https://orcid.org/0000-0001-5827-3552 en_US http://dx.doi.org/10.1021/om500655n Organometallics Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Hoveyda, Amir H. Townsend, Erik M. Hyvl, Jakub Forrest Jr, William P Schrock, Richard Royce Mueller, Peter Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands |
| title | Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands |
| title_full | Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands |
| title_fullStr | Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands |
| title_full_unstemmed | Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands |
| title_short | Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands |
| title_sort | synthesis of molybdenum and tungsten alkylidene complexes that contain sterically demanding arenethiolate ligands |
| url | http://hdl.handle.net/1721.1/109366 https://orcid.org/0000-0001-5827-3552 |
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