dc.contributor.author | Gerber, Laura C. H. | |
dc.contributor.author | Schrock, Richard Royce | |
dc.contributor.author | Mueller, Peter | |
dc.date.accessioned | 2014-04-11T14:09:10Z | |
dc.date.available | 2014-04-11T14:09:10Z | |
dc.date.issued | 2013-04 | |
dc.date.submitted | 2013-01 | |
dc.identifier.issn | 0276-7333 | |
dc.identifier.issn | 1520-6041 | |
dc.identifier.uri | http://hdl.handle.net/1721.1/86098 | |
dc.description.abstract | Molybdenum and tungsten bispyrrolide alkylidene complexes that contain a 2,6-dimesitylphenylimido (NAr*) ligand have been prepared, in which the pyrrolide is the parent pyrrolide or 2,5-dimethylpyrrolide. Monoalkoxide pyrrolide (MAP) complexes were prepared through addition of 1 equiv of an alcohol to the bispyrrolide complexes. MAP compounds that contain the parent pyrrolide (NC[subscript 4]H[– over 4]) are pyridine adducts, while those that contain 2,5-dimethylpyrrolide are pyridine free. Molybdenum and tungsten MAP 2,5-dimethylpyrrolide complexes that contain O-t-Bu, OCMe(CF[subscript 3])[subscript 2], or O-2,6-Me[subscript 2]C[subscript 6]H[subscript 3] ligands were found to have approximately equal amounts of syn and anti alkylidene isomers, which allowed a study of the interconversion of the two employing [superscript 1]H–[superscript 1]H EXSY methods. The K[subscript eq] values ([syn]/[anti]) are all 2–3 orders of magnitude smaller than those observed for a large number of Mo bisalkoxide imido alkylidene complexes, as a consequence of the destabilization of the syn isomer by the sterically demanding NAr* ligand. The rates of interconversion of syn and anti isomers were found to be 1–2 orders of magnitude faster for W MAP complexes than for Mo MAP complexes. | en_US |
dc.description.sponsorship | National Science Foundation (U.S.) (CHE-1111133) | en_US |
dc.description.sponsorship | National Science Foundation (U.S.) (CHE-9808061) | en_US |
dc.description.sponsorship | National Science Foundation (U.S.) (CHE-0946721) | en_US |
dc.language.iso | en_US | |
dc.publisher | American Chemical Society (ACS) | en_US |
dc.relation.isversionof | http://dx.doi.org/10.1021/om4000693 | en_US |
dc.rights | 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. | en_US |
dc.source | Prof. Schrock via Erja Kajosalo | en_US |
dc.title | Molybdenum and Tungsten Monoalkoxide Pyrrolide (MAP) Alkylidene Complexes That Contain a 2,6-Dimesitylphenylimido Ligand | en_US |
dc.type | Article | en_US |
dc.identifier.citation | Gerber, Laura C. H., Richard R. Schrock, and Peter Müller. “Molybdenum and Tungsten Monoalkoxide Pyrrolide (MAP) Alkylidene Complexes That Contain a 2,6-Dimesitylphenylimido Ligand.” Organometallics 32, no. 8 (April 22, 2013): 2373–2378. | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemistry | en_US |
dc.contributor.approver | Schrock, Richard Royce | en_US |
dc.contributor.mitauthor | Gerber, Laura C. H. | en_US |
dc.contributor.mitauthor | Schrock, Richard Royce | en_US |
dc.contributor.mitauthor | Mueller, Peter | en_US |
dc.relation.journal | Organometallics | en_US |
dc.eprint.version | Author's final manuscript | en_US |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | en_US |
eprint.status | http://purl.org/eprint/status/PeerReviewed | en_US |
dspace.orderedauthors | Gerber, Laura C. H.; Schrock, Richard R.; Müller, Peter | en_US |
dc.identifier.orcid | https://orcid.org/0000-0001-5827-3552 | |
mit.license | PUBLISHER_POLICY | en_US |
mit.metadata.status | Complete | |