Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes
Reactions between Mo(NAr)(CHR)(Me[subscript 2]Pyr)(OTPP) (Ar = 2,6-i-Pr[subscript 2]C[subscript 6]H[subscript 3], R = H or CHCMe[subscript 2]Ph, Me[subscript 2]Pyr = 2,5-dimethylpyrrolide, OTPP = O-2,3,5,6-Ph[subscript 4]C[subscript 6]H) and CH[subscript 2]═CHX where X = B(pin), SiMe[subscript 3], N...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2014
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| Online Access: | http://hdl.handle.net/1721.1/88577 https://orcid.org/0000-0001-5827-3552 |
| _version_ | 1811094458081476608 |
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| author | Townsend, Erik M. Kilyanek, Stefan M. Smith, Stacey J. Hoveyda, Amir H. Schrock, Richard Royce Mueller, Peter |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Townsend, Erik M. Kilyanek, Stefan M. Smith, Stacey J. Hoveyda, Amir H. Schrock, Richard Royce Mueller, Peter |
| author_sort | Townsend, Erik M. |
| collection | MIT |
| description | Reactions between Mo(NAr)(CHR)(Me[subscript 2]Pyr)(OTPP) (Ar = 2,6-i-Pr[subscript 2]C[subscript 6]H[subscript 3], R = H or CHCMe[subscript 2]Ph, Me[subscript 2]Pyr = 2,5-dimethylpyrrolide, OTPP = O-2,3,5,6-Ph[subscript 4]C[subscript 6]H) and CH[subscript 2]═CHX where X = B(pin), SiMe[subscript 3], N-carbazolyl, N-pyrrolidinonyl, PPh[subscript 2], OPr, or SPh lead to Mo(NAr)(CHX)(Me[subscript 2]Pyr)(OTPP) complexes in good yield. All have been characterized through X-ray studies (as an acetonitrile adduct in the case of X = PPh[subscript 2]). The efficiencies of metathesis reactions initiated by Mo(NAr)(CHX)(Me[subscript 2]Pyr)(OTPP) complexes can be rationalized on the basis of steric factors; electronic differences imposed as a consequence of X being bound to the alkylidene carbon do not seem to play a major role. Side reactions that promote catalyst decomposition do not appear to be a serious limitation for Mo═CHX species. |
| first_indexed | 2024-09-23T16:00:23Z |
| format | Article |
| id | mit-1721.1/88577 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T16:00:23Z |
| publishDate | 2014 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/885772022-10-02T05:40:59Z Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes Townsend, Erik M. Kilyanek, Stefan M. Smith, Stacey J. Hoveyda, Amir H. Schrock, Richard Royce Mueller, Peter Massachusetts Institute of Technology. Department of Chemistry Schrock, Richard Royce Townsend, Erik M. Kilyanek, Stefan M. Schrock, Richard Royce Mueller, Peter Smith, Stacey J. Reactions between Mo(NAr)(CHR)(Me[subscript 2]Pyr)(OTPP) (Ar = 2,6-i-Pr[subscript 2]C[subscript 6]H[subscript 3], R = H or CHCMe[subscript 2]Ph, Me[subscript 2]Pyr = 2,5-dimethylpyrrolide, OTPP = O-2,3,5,6-Ph[subscript 4]C[subscript 6]H) and CH[subscript 2]═CHX where X = B(pin), SiMe[subscript 3], N-carbazolyl, N-pyrrolidinonyl, PPh[subscript 2], OPr, or SPh lead to Mo(NAr)(CHX)(Me[subscript 2]Pyr)(OTPP) complexes in good yield. All have been characterized through X-ray studies (as an acetonitrile adduct in the case of X = PPh[subscript 2]). The efficiencies of metathesis reactions initiated by Mo(NAr)(CHX)(Me[subscript 2]Pyr)(OTPP) complexes can be rationalized on the basis of steric factors; electronic differences imposed as a consequence of X being bound to the alkylidene carbon do not seem to play a major role. Side reactions that promote catalyst decomposition do not appear to be a serious limitation for Mo═CHX species. National Science Foundation (U.S.) (CHE-1111133) National Institutes of Health (U.S.) (Grant GM-59426) 2014-08-07T14:57:07Z 2014-08-07T14:57:07Z 2013-08 2013-06 Article http://purl.org/eprint/type/JournalArticle 0276-7333 1520-6041 http://hdl.handle.net/1721.1/88577 Townsend, Erik M., Stefan M. Kilyanek, Richard R. Schrock, Peter Mueller, Stacey J. Smith, and Amir H. Hoveyda. “High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes.” Organometallics 32, no. 16 (August 26, 2013): 4612–4617. https://orcid.org/0000-0001-5827-3552 en_US http://dx.doi.org/10.1021/om400584f 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) Prof. Schrock via Erja Kajosalo |
| spellingShingle | Townsend, Erik M. Kilyanek, Stefan M. Smith, Stacey J. Hoveyda, Amir H. Schrock, Richard Royce Mueller, Peter Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes |
| title | Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes |
| title_full | Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes |
| title_fullStr | Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes |
| title_full_unstemmed | Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes |
| title_short | Synthesis of High Oxidation State Molybdenum Imido Heteroatom-Substituted Alkylidene Complexes |
| title_sort | synthesis of high oxidation state molybdenum imido heteroatom substituted alkylidene complexes |
| url | http://hdl.handle.net/1721.1/88577 https://orcid.org/0000-0001-5827-3552 |
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