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NMR scale reactions of6+11\u219212mediated by complex2at 120 \u00b0C results in 50% conversion after 24 h with 2\u00d7 excess alkyne while resulting in 95% conversion with 3\u00d7 excess alkyne."},{"key":"ref25\/cit25a","doi-asserted-by":"crossref","DOI":"10.1002\/0470010088","volume-title":"Lanthanide and Actinide Chemistry","author":"Cotton S.","year":"2006"},{"key":"ref25\/cit25b","doi-asserted-by":"crossref","first-page":"1122","DOI":"10.1021\/ja043415j","volume":"127","author":"Li H. X.","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref25\/cit25c","volume-title":"Chemistry of the f-Block Elements","author":"Aspinall H. C.","year":"2001"},{"key":"ref25\/cit25d","doi-asserted-by":"crossref","first-page":"5396","DOI":"10.1021\/ic9800684","volume":"37","author":"Aspinall H. C.","year":"1998","journal-title":"Inorg. Chem."},{"key":"ref25\/cit25e","volume-title":"Science","volume":"217","author":"Marks T. 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The mixture of Zr(NMe2)4(5) and benzylmercaptan (16) more slowly produces a bright orange precipitate under identical conditions."},{"key":"ref30\/cit30","doi-asserted-by":"crossref","first-page":"911","DOI":"10.1021\/om00106a009","volume":"8","author":"Erker G.","year":"1989","journal-title":"Organometallics"},{"key":"ref31\/cit31","doi-asserted-by":"crossref","first-page":"2804","DOI":"10.1021\/ic00115a005","volume":"34","author":"Heyn R. H.","year":"1995","journal-title":"Inorg. Chem."},{"key":"ref32\/cit32","doi-asserted-by":"crossref","first-page":"3024","DOI":"10.1021\/ja809436y","volume":"131","author":"Fritzinger B.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref33\/cit33","doi-asserted-by":"crossref","first-page":"1940","DOI":"10.1039\/j19680001940","author":"Chandra G.","year":"1968","journal-title":"J. Chem. Soc. A"},{"key":"ref34\/cit34a","doi-asserted-by":"crossref","first-page":"2121","DOI":"10.1021\/ja00985a024","volume":"89","author":"Gregory M. 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The present study finds that CH3D gives a triplet at 0.14 ppm in the1H NMR."},{"key":"ref39\/cit39a","doi-asserted-by":"crossref","first-page":"573","DOI":"10.1021\/om8008684","volume":"28","author":"Roering A. J.","year":"2009","journal-title":"Organometallics"},{"key":"ref39\/cit39b","doi-asserted-by":"crossref","first-page":"5580","DOI":"10.1002\/anie.200701816","volume":"46","author":"Hoyt H. M.","year":"2007","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref39\/cit39c","doi-asserted-by":"crossref","first-page":"101","DOI":"10.1016\/j.molcata.2003.10.053","volume":"213","author":"Nishiura M.","year":"2004","journal-title":"J. Mol. Catal. A: Chem."},{"key":"ref39\/cit39d","doi-asserted-by":"crossref","first-page":"183","DOI":"10.1016\/S0020-1693(02)00798-3","volume":"334","author":"Wang J.","year":"2002","journal-title":"Inorg. Chim. Acta"},{"key":"ref39\/cit39e","doi-asserted-by":"crossref","first-page":"4724","DOI":"10.1021\/om990655c","volume":"18","author":"Dash A. K.","year":"1999","journal-title":"Organometallics"},{"key":"ref40\/cit40","doi-asserted-by":"crossref","first-page":"5471","DOI":"10.1021\/jo901045g","volume":"74","author":"Tobisu M.","year":"2009","journal-title":"J. Org. Chem."},{"key":"ref41\/cit41","unstructured":"In addition to NMR, the formation of31and31-D(E\/Z)are also confirmed by HRMS. We are unable to support the formation of31-D2by HRMS due to an overlapping13C isotopic pattern."},{"key":"ref42\/cit42","unstructured":"Stereochemical assignment of product vinyl proton resonances were determined by 1D NOESY NMR spectroscopy. For 1D NOESY NMR and2H NMR spectra, seeSupporting Information."},{"key":"ref43\/cit43","unstructured":"Injecting ethanethiol-d(7-d) into a completed reaction did not result in deuterium incorporation into an already formed product."},{"key":"ref44\/cit44","doi-asserted-by":"crossref","first-page":"3645","DOI":"10.1021\/ic00095a006","volume":"33","author":"Coucouvanis D.","year":"1994","journal-title":"Inorg. Chem."},{"key":"ref45\/cit45a","doi-asserted-by":"crossref","first-page":"823","DOI":"10.1016\/j.poly.2005.07.009","volume":"25","author":"Robertson S. D.","year":"2006","journal-title":"Polyhedron"},{"key":"ref45\/cit45b","doi-asserted-by":"crossref","first-page":"1496","DOI":"10.1021\/ic991402e","volume":"39","author":"Friese J. C.","year":"2000","journal-title":"Inorg. Chem."},{"key":"ref45\/cit45c","doi-asserted-by":"crossref","first-page":"227","DOI":"10.1016\/S0020-1693(97)06099-4","volume":"270","author":"Ashby M. T.","year":"1998","journal-title":"Inorg. Chem. 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Chem."},{"key":"ref50\/cit50","unstructured":"This diminished activity has been attributed to the greater H\u2212S bond enthalpies; see ref5i."},{"key":"ref51\/cit51","doi-asserted-by":"crossref","first-page":"4725","DOI":"10.1021\/om960396g","volume":"15","author":"Fandos R.","year":"1996","journal-title":"Organometallics"},{"key":"ref52\/cit52a","doi-asserted-by":"crossref","first-page":"531","DOI":"10.1021\/om0508785","volume":"25","author":"Kissounko D.","year":"2006","journal-title":"Organometallics"},{"key":"ref52\/cit52b","doi-asserted-by":"crossref","first-page":"1153","DOI":"10.1021\/om0006559","volume":"20","author":"O\u2019Connor P. 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Soc."},{"key":"ref60\/cit60","doi-asserted-by":"crossref","first-page":"3158","DOI":"10.1021\/om00032a044","volume":"12","author":"Hou Z.","year":"1993","journal-title":"Organometallics"},{"key":"ref61\/cit61","unstructured":"Organozirconium complexes are known from the literature to cleave thiol C\u2212S bonds; however, corresponding alkene products, indicative of this process, were not been observed by1H NMR or GC\/MS."},{"key":"ref62\/cit62","unstructured":"The catalytic cycle is presented here with a monomeric organozirconium complex for simplicity. SeeSupporting Informationfor a dimer catalytic cycle."},{"key":"ref63\/cit63a","doi-asserted-by":"crossref","first-page":"1996","DOI":"10.1021\/ja8084302","volume":"131","author":"Ugolotti J.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref63\/cit63b","doi-asserted-by":"crossref","first-page":"1093","DOI":"10.1021\/jo702306k","volume":"73","author":"Albert B. J.","year":"2008","journal-title":"J. Org. Chem."},{"key":"ref63\/cit63c","doi-asserted-by":"crossref","first-page":"1605","DOI":"10.1002\/anie.199416051","volume":"33","author":"Rosenthal U.","year":"1994","journal-title":"Angew. Chem., Int. Ed. Engl."},{"key":"ref64\/cit64","unstructured":"Protonolysis is typically rapid in reports of organozirconium- and organo-f-element-mediated hydroelementation (refs8h,n); however, organolanthanide-catalyzed hydrophosphination (refs9f\u2212h) appears to have a more sluggish product protonolysis from the metal center, resulting in turnover-limiting protonolysis."}],"container-title":["Journal of the American Chemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/ja103979b","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,4,3]],"date-time":"2023-04-03T19:54:32Z","timestamp":1680551672000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/ja103979b"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2010,7,9]]},"references-count":167,"journal-issue":{"issue":"30","published-print":{"date-parts":[[2010,8,4]]}},"alternative-id":["10.1021\/ja103979b"],"URL":"https:\/\/doi.org\/10.1021\/ja103979b","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2010,7,9]]}}}