Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum
In this paper we describe the syntheses of several new stereogenic-at-metal imido alkylidene complexes of molybdenum, Mo(NR)(CHR′)(X)(Y), many of which had to be prepared through selective nucleophilic displacement reactions in imido alkylidene complexes. The reported compounds include Mo(NAd)(CHCMe...
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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/1721.1/84113 https://orcid.org/0000-0001-5827-3552 |
| _version_ | 1826198189335642112 |
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| author | Marinescu, Smaranda C. Ng, Victor Wee Lin Lichtscheidl, Alejandro G. Takase, Michael K. Schrock, Richard Royce Mueller, Peter |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Marinescu, Smaranda C. Ng, Victor Wee Lin Lichtscheidl, Alejandro G. Takase, Michael K. Schrock, Richard Royce Mueller, Peter |
| author_sort | Marinescu, Smaranda C. |
| collection | MIT |
| description | In this paper we describe the syntheses of several new stereogenic-at-metal imido alkylidene complexes of molybdenum, Mo(NR)(CHR′)(X)(Y), many of which had to be prepared through selective nucleophilic displacement reactions in imido alkylidene complexes. The reported compounds include Mo(NAd)(CHCMe[subscript 2]Ph)(MesPyr)[subscript 2] (1a; MesPyr = 2-mesitylpyrrolide, Ad = 1-adamantyl), Mo(NAd)(CHCMe[subscript 2]Ph)(2-CNPyr)[subscript 2] (1b; 2-CNPyr = 2-cyanopyrrolide), Mo(NAd)(CHCMe[subscript 2]Ph)(MesPyr)(OTPP) (2a; OTPP = 2,3,5,6-tetraphenylphenoxide), Mo(NAd)(CHCMe[subscript 2]Ph)(MesPyr)(OBr[subscript 2]Bitet) (2b; OBr[subscript 2]Bitet = (R)-3,3′-dibromo-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-olate), Mo(NAd)(CHCMe[subscript 2]Ph)(OHIPT)(2-Mespyr) (2c; HIPT = 2,6-(2,4,6-iPr[subscript 3]C[subscript 6]H[subscript 2])[subscript 2]C[subscript 6]H[subscript 3]), Mo(NAd)(CHCMe[subscript 2]Ph)(OTf)(OHIPT) (3), Mo(NAd)(CHCMe[subscript 2]Ph)(OTf)(OHIPT)(PMe[subscript 3]) (3(PMe[subscript 3])), Mo(NAd)(CHCMe[subscript 2]Ph)(2-CNPyr)(OHIPT) (4), Mo(NAd)(CHCMe[subscript 2]Ph)(OHIPT)(OCMe[subscript 3]) (5), Mo(NR)(CHCMe[subscript 2]Ph)(OR[subscript F6])(OHMT) (OR[subscript F6] = OCMe(CF[subscript 3])[subscript 2]; HMT = 2,6-Mes[subscript 2]C[subscript 6]H[subscript 3]; R = 2,6-iPr[subscript 2]C[subscript 6]H[subscript 3] (Ar, 6a), 2,6-Me[subscript 2]C[subscript 6]H[subscript 3] (Ar′, 6b), 2-iPrC[subscript 6]H[subscript 4] (Ar[sueprscript iPr], 6c), Ad (6d)), Mo(NR)(CHCMe[subscript 2]Ph)(OR[subscript F6])[N(H)HMT] (7a (R = Ar′) and 7b (R = Ar[superscript iPr])), and Mo(NAd)(CHCMe[subscript 2]Ph)(OR[subscript F6])(HMT) (8). X-ray structural studies were carried out on 1b, 2a–c, 3(PMe[subscript 3]), 4, 5, 6d, 7b, and 8. Compound 1b is an octamer in which two η[superscript 1]-pyrrolides are trans to one another at each metal center and cyano groups bind from neighboring Mo centers trans to the alkylidene and imido ligands. |
| first_indexed | 2024-09-23T11:00:33Z |
| format | Article |
| id | mit-1721.1/84113 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T11:00:33Z |
| publishDate | 2014 |
| publisher | American Chemical Society (ACS) |
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| spelling | mit-1721.1/841132022-09-27T16:29:10Z Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum Marinescu, Smaranda C. Ng, Victor Wee Lin Lichtscheidl, Alejandro G. Takase, Michael K. Schrock, Richard Royce Mueller, Peter Massachusetts Institute of Technology. Department of Chemistry Schrock, Richard Royce Marinescu, Smaranda C. Ng, Victor Wee Lin Lichtscheidl, Alejandro G. Schrock, Richard Royce Mueller, Peter Takase, Michael K. In this paper we describe the syntheses of several new stereogenic-at-metal imido alkylidene complexes of molybdenum, Mo(NR)(CHR′)(X)(Y), many of which had to be prepared through selective nucleophilic displacement reactions in imido alkylidene complexes. The reported compounds include Mo(NAd)(CHCMe[subscript 2]Ph)(MesPyr)[subscript 2] (1a; MesPyr = 2-mesitylpyrrolide, Ad = 1-adamantyl), Mo(NAd)(CHCMe[subscript 2]Ph)(2-CNPyr)[subscript 2] (1b; 2-CNPyr = 2-cyanopyrrolide), Mo(NAd)(CHCMe[subscript 2]Ph)(MesPyr)(OTPP) (2a; OTPP = 2,3,5,6-tetraphenylphenoxide), Mo(NAd)(CHCMe[subscript 2]Ph)(MesPyr)(OBr[subscript 2]Bitet) (2b; OBr[subscript 2]Bitet = (R)-3,3′-dibromo-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2-olate), Mo(NAd)(CHCMe[subscript 2]Ph)(OHIPT)(2-Mespyr) (2c; HIPT = 2,6-(2,4,6-iPr[subscript 3]C[subscript 6]H[subscript 2])[subscript 2]C[subscript 6]H[subscript 3]), Mo(NAd)(CHCMe[subscript 2]Ph)(OTf)(OHIPT) (3), Mo(NAd)(CHCMe[subscript 2]Ph)(OTf)(OHIPT)(PMe[subscript 3]) (3(PMe[subscript 3])), Mo(NAd)(CHCMe[subscript 2]Ph)(2-CNPyr)(OHIPT) (4), Mo(NAd)(CHCMe[subscript 2]Ph)(OHIPT)(OCMe[subscript 3]) (5), Mo(NR)(CHCMe[subscript 2]Ph)(OR[subscript F6])(OHMT) (OR[subscript F6] = OCMe(CF[subscript 3])[subscript 2]; HMT = 2,6-Mes[subscript 2]C[subscript 6]H[subscript 3]; R = 2,6-iPr[subscript 2]C[subscript 6]H[subscript 3] (Ar, 6a), 2,6-Me[subscript 2]C[subscript 6]H[subscript 3] (Ar′, 6b), 2-iPrC[subscript 6]H[subscript 4] (Ar[sueprscript iPr], 6c), Ad (6d)), Mo(NR)(CHCMe[subscript 2]Ph)(OR[subscript F6])[N(H)HMT] (7a (R = Ar′) and 7b (R = Ar[superscript iPr])), and Mo(NAd)(CHCMe[subscript 2]Ph)(OR[subscript F6])(HMT) (8). X-ray structural studies were carried out on 1b, 2a–c, 3(PMe[subscript 3]), 4, 5, 6d, 7b, and 8. Compound 1b is an octamer in which two η[superscript 1]-pyrrolides are trans to one another at each metal center and cyano groups bind from neighboring Mo centers trans to the alkylidene and imido ligands. National Science Foundation (U.S.) (CHE-0841187) National Science Foundation (U.S.) (CHE-0946721) National Science Foundation (U.S.) (CHE-111133) National Science Foundation (U.S.) (CHE-9808061) 2014-01-21T18:16:19Z 2014-01-21T18:16:19Z 2012-08 2012-06 Article http://purl.org/eprint/type/JournalArticle 0276-7333 1520-6041 http://hdl.handle.net/1721.1/84113 Marinescu, Smaranda C., Victor W. L. Ng, Alejandro G. Lichtscheidl, Richard R. Schrock, Peter Müller, and Michael K. Takase. “Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum.” Organometallics 31, no. 17 (September 10, 2012): 6336-6343. https://orcid.org/0000-0001-5827-3552 en_US http://dx.doi.org/10.1021/om300585s 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 | Marinescu, Smaranda C. Ng, Victor Wee Lin Lichtscheidl, Alejandro G. Takase, Michael K. Schrock, Richard Royce Mueller, Peter Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum |
| title | Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum |
| title_full | Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum |
| title_fullStr | Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum |
| title_full_unstemmed | Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum |
| title_short | Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum |
| title_sort | syntheses of variations of stereogenic at metal imido alkylidene complexes of molybdenum |
| url | http://hdl.handle.net/1721.1/84113 https://orcid.org/0000-0001-5827-3552 |
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