Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes
Seven bipyridine adducts of molybdenum imido alkylidene bispyrrolide complexes of the type Mo(NR)(CHCMe[subscript 2]R′)(Pyr)[subscript 2](bipy) (1a–1g; R = 2,6-i-Pr[subscript 2]C[subscript 6]H[subscript 3] (Ar), adamantyl (Ad), 2,6-Me[subscript 2]C[subscript 6]H[subscript 3] (Ar′), 2-i-PrC[subscript...
| Main Authors: | , , , , , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2013
|
| Online Access: | http://hdl.handle.net/1721.1/82560 https://orcid.org/0000-0001-5827-3552 |
| _version_ | 1826189085620830208 |
|---|---|
| author | Lichtscheidl, Alejandro G. Ng, Victor Wee Lin Takase, Michael K. Malcolmson, Steven J. Meek, Simon J. Li, Bo Kiesewetter, Elizabeth T. Hoveyda, Amir H. Muller, Peter Schrock, Richard Royce |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Lichtscheidl, Alejandro G. Ng, Victor Wee Lin Takase, Michael K. Malcolmson, Steven J. Meek, Simon J. Li, Bo Kiesewetter, Elizabeth T. Hoveyda, Amir H. Muller, Peter Schrock, Richard Royce |
| author_sort | Lichtscheidl, Alejandro G. |
| collection | MIT |
| description | Seven bipyridine adducts of molybdenum imido alkylidene bispyrrolide complexes of the type Mo(NR)(CHCMe[subscript 2]R′)(Pyr)[subscript 2](bipy) (1a–1g; R = 2,6-i-Pr[subscript 2]C[subscript 6]H[subscript 3] (Ar), adamantyl (Ad), 2,6-Me[subscript 2]C[subscript 6]H[subscript 3] (Ar′), 2-i-PrC[subscript 6]H[subscript 4] (Ar[superscript iPr]), 2-ClC[subscript 6]H[subscript 4] (Ar[superscript Cl]), 2-t-BuC[subscript 6]H[subscript 4] (Ar[superscript tBu]), and 2-MesitylC[subscript 6]H[subscript 4] (Ar[superscript M]), respectively; R′ = Me, Ph) have been prepared using three different methods. Up to three isomers of the adducts are observed that are proposed to be the trans- and two possible cis-pyrrolide isomers of syn-alkylidenes. Sonication of a mixture containing 1a–1g, HMTOH (2,6-dimesitylphenol), and ZnCl[subscript 2](dioxane) led to the formation of MAP species of the type Mo(NR)(CHCMe[subscript 2]R′)(Pyr)(OHMT) (3a–3g). DCMNBD (2,3-dicarbomethoxynorbornadiene) is polymerized employing 3a–3g as initiators to yield >98% cis,syndiotactic poly(DCMNBD). Attempts to prepare bipy adducts of bisdimethylpyrrolide complexes led to the formation of imido alkylidyne complexes of the type Mo(NR)(CCMe[subscript 2]R′)(Me[subscript 2]Pyr)(bipy) (Me[subscript 2]Pyr = 2,5-dimethylpyrrolide; 4a–4g) through a ligand-induced migration of an alkylidene α proton to a dimethylpyrrolide ligand. X-ray structures of Mo(NAr)(CHCMe[subscript 2]Ph)(Pyr)[subscript 2](bipy) (1a), Mo(NAr[superscript iPr])(CHCMe[subscript 2]Ph)(Pyr)(OHMT) (3d), Mo(NAr)(CCMe[subscript 2]Ph)(Me[subscript 2]Pyr)(bipy) (4a), the NAr′ analog of 4a (4c), and Mo(NAr[superscript T])(CCMe[subscript 3])(Me[subscript 2]Pyr)(bipy) (Ar[superscript T] = 2-(2,4,6-i-Pr[subscript 3]C[subscript 6]H[subscript 2])C[subscript 6]H[subscript 4]; 4g) showed normal bond lengths and angles. |
| first_indexed | 2024-09-23T08:09:19Z |
| format | Article |
| id | mit-1721.1/82560 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T08:09:19Z |
| publishDate | 2013 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/825602022-09-23T11:15:21Z Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes Lichtscheidl, Alejandro G. Ng, Victor Wee Lin Takase, Michael K. Malcolmson, Steven J. Meek, Simon J. Li, Bo Kiesewetter, Elizabeth T. Hoveyda, Amir H. Muller, Peter Schrock, Richard Royce Massachusetts Institute of Technology. Department of Chemistry Lichtscheidl, Alejandro G. Ng, Victor Wee Lin Muller, Peter Takase, Michael K. Schrock, Richard Royce Seven bipyridine adducts of molybdenum imido alkylidene bispyrrolide complexes of the type Mo(NR)(CHCMe[subscript 2]R′)(Pyr)[subscript 2](bipy) (1a–1g; R = 2,6-i-Pr[subscript 2]C[subscript 6]H[subscript 3] (Ar), adamantyl (Ad), 2,6-Me[subscript 2]C[subscript 6]H[subscript 3] (Ar′), 2-i-PrC[subscript 6]H[subscript 4] (Ar[superscript iPr]), 2-ClC[subscript 6]H[subscript 4] (Ar[superscript Cl]), 2-t-BuC[subscript 6]H[subscript 4] (Ar[superscript tBu]), and 2-MesitylC[subscript 6]H[subscript 4] (Ar[superscript M]), respectively; R′ = Me, Ph) have been prepared using three different methods. Up to three isomers of the adducts are observed that are proposed to be the trans- and two possible cis-pyrrolide isomers of syn-alkylidenes. Sonication of a mixture containing 1a–1g, HMTOH (2,6-dimesitylphenol), and ZnCl[subscript 2](dioxane) led to the formation of MAP species of the type Mo(NR)(CHCMe[subscript 2]R′)(Pyr)(OHMT) (3a–3g). DCMNBD (2,3-dicarbomethoxynorbornadiene) is polymerized employing 3a–3g as initiators to yield >98% cis,syndiotactic poly(DCMNBD). Attempts to prepare bipy adducts of bisdimethylpyrrolide complexes led to the formation of imido alkylidyne complexes of the type Mo(NR)(CCMe[subscript 2]R′)(Me[subscript 2]Pyr)(bipy) (Me[subscript 2]Pyr = 2,5-dimethylpyrrolide; 4a–4g) through a ligand-induced migration of an alkylidene α proton to a dimethylpyrrolide ligand. X-ray structures of Mo(NAr)(CHCMe[subscript 2]Ph)(Pyr)[subscript 2](bipy) (1a), Mo(NAr[superscript iPr])(CHCMe[subscript 2]Ph)(Pyr)(OHMT) (3d), Mo(NAr)(CCMe[subscript 2]Ph)(Me[subscript 2]Pyr)(bipy) (4a), the NAr′ analog of 4a (4c), and Mo(NAr[superscript T])(CCMe[subscript 3])(Me[subscript 2]Pyr)(bipy) (Ar[superscript T] = 2-(2,4,6-i-Pr[subscript 3]C[subscript 6]H[subscript 2])C[subscript 6]H[subscript 4]; 4g) showed normal bond lengths and angles. National Science Foundation (U.S.) (CHE-0841187) National Science Foundation (U.S.) (CHE-1111133) United States. Dept. of Energy (DE-FG02-86ER13564) National Institutes of Health (U.S.) (GM-59426) 2013-11-22T20:10:01Z 2013-11-22T20:10:01Z 2012-06 2012-04 Article http://purl.org/eprint/type/JournalArticle 0276-7333 1520-6041 http://hdl.handle.net/1721.1/82560 Lichtscheidl, Alejandro G., Victor W. L. Ng, Peter Müller, Michael K. Takase, Richard R. Schrock, Steven J. Malcolmson, Simon J. Meek, Bo Li, Elizabeth T. Kiesewetter, and Amir H. Hoveyda. “Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes.” Organometallics 31, no. 12 (June 25, 2012): 4558-4564. https://orcid.org/0000-0001-5827-3552 en_US http://dx.doi.org/10.1021/om300353e 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) PMC |
| spellingShingle | Lichtscheidl, Alejandro G. Ng, Victor Wee Lin Takase, Michael K. Malcolmson, Steven J. Meek, Simon J. Li, Bo Kiesewetter, Elizabeth T. Hoveyda, Amir H. Muller, Peter Schrock, Richard Royce Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes |
| title | Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes |
| title_full | Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes |
| title_fullStr | Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes |
| title_full_unstemmed | Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes |
| title_short | Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes |
| title_sort | bipyridine adducts of molybdenum imido alkylidene and imido alkylidyne complexes |
| url | http://hdl.handle.net/1721.1/82560 https://orcid.org/0000-0001-5827-3552 |
| work_keys_str_mv | AT lichtscheidlalejandrog bipyridineadductsofmolybdenumimidoalkylideneandimidoalkylidynecomplexes AT ngvictorweelin bipyridineadductsofmolybdenumimidoalkylideneandimidoalkylidynecomplexes AT takasemichaelk bipyridineadductsofmolybdenumimidoalkylideneandimidoalkylidynecomplexes AT malcolmsonstevenj bipyridineadductsofmolybdenumimidoalkylideneandimidoalkylidynecomplexes AT meeksimonj bipyridineadductsofmolybdenumimidoalkylideneandimidoalkylidynecomplexes AT libo bipyridineadductsofmolybdenumimidoalkylideneandimidoalkylidynecomplexes AT kiesewetterelizabetht bipyridineadductsofmolybdenumimidoalkylideneandimidoalkylidynecomplexes AT hoveydaamirh bipyridineadductsofmolybdenumimidoalkylideneandimidoalkylidynecomplexes AT mullerpeter bipyridineadductsofmolybdenumimidoalkylideneandimidoalkylidynecomplexes AT schrockrichardroyce bipyridineadductsofmolybdenumimidoalkylideneandimidoalkylidynecomplexes |