Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum
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Author(s)
Marinescu, Smaranda C.
Ng, Victor Wee Lin
Lichtscheidl, Alejandro G.
Takase, Michael K.
Schrock, Richard Royce
Mueller, Peter
Date Issued
August 2012
Journal
Organometallics
Publisher
American Chemical Society (ACS)
Citation
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.
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Author's final manuscript
Abstract
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/om300585s
