{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T19:51:09Z","timestamp":1760385069472,"version":"build-2065373602"},"reference-count":74,"publisher":"Wiley","issue":"28","license":[{"start":{"date-parts":[[2010,6,11]],"date-time":"2010-06-11T00:00:00Z","timestamp":1276214400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2010,7,26]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>An alkyne tetracarbonyl dicobalt complex with a chelated phosphine\u2013alkene ligand, in which the phosphorus atom and the alkene from the ligand are attached to the same cobalt atom has been prepared, isolated, and characterized by X\u2010ray crystallography. The complex serves as a mechanistic model for an intermediate of the Pauson\u2013Khand (PK) reaction. Although the alkene fragment is located in an equatorial coordination site with an appropriate orientation, and, therefore, should undergo insertion, it failed to give the PK product upon either thermal or <jats:italic>N<\/jats:italic>\u2010methylmorpholine <jats:italic>N<\/jats:italic>\u2010oxide activation. However, a phosphine\u2013alkene complex that contains a terminal alkene readily provided the corresponding PK product. We attribute this change in reactivity to the different ability of each olefin to undergo 1,2\u2010insertion. These results provide further insights into the factors that govern a crucial step in the PK reaction, the olefin insertion.<\/jats:p>","DOI":"10.1002\/chem.201000357","type":"journal-article","created":{"date-parts":[[2010,6,11]],"date-time":"2010-06-11T12:46:09Z","timestamp":1276260369000},"page":"8340-8346","source":"Crossref","is-referenced-by-count":11,"title":["Phosphine\u2013Alkene Ligands as Mechanistic Probes in the Pauson\u2013Khand Reaction"],"prefix":"10.1002","volume":"16","author":[{"given":"Catalina","family":"Ferrer","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jordi","family":"Benet\u2010Buchholz","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Antoni","family":"Riera","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xavier","family":"Verdaguer","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2010,7,19]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For general reviews see:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-2005-918922"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200462235"},{"key":"e_1_2_6_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200462235"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200200547"},{"key":"e_1_2_6_4_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200200547"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2004.06.072"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200600328"},{"key":"e_1_2_6_7_2","first-page":"26","author":"Rivero M. 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These data can be obtained free of charge from The Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk\/data_request\/cif."},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200703612"},{"key":"e_1_2_6_45_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200703612"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1039\/a801003j"},{"key":"e_1_2_6_47_2","unstructured":"\u00a0"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/om060935"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo982245o"},{"key":"e_1_2_6_50_2","unstructured":"Compound8crystallized in the form of extremely small crystals (with axes <10\u2005\u03bcm). After several attempts a crystal plate with the dimensions 0.048\u00d70.019\u00d70.010\u2005\u03bcm3could be used. The obtained data are of low resolution (2\u03b8max: 27\u00b0) and are not complete (80\u2009%) but it was considered that the structure was of high enough quality to confirm the identity of compound8. Compound8crystallizes with half a molecule in the unit cell (Cisymmetry). 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