{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,3]],"date-time":"2026-10-03T08:57:31Z","timestamp":1791017851635,"version":"4.1.0"},"reference-count":47,"publisher":"Wiley","issue":"39","license":[{"start":{"date-parts":[[2013,8,9]],"date-time":"2013-08-09T00:00:00Z","timestamp":1376006400000},"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":[[2013,9,23]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A series of 2,4,6\u2010triarylphosphinines were prepared and investigated in the base\u2010assisted cyclometalation reaction using [Cp*IrCl<jats:sub>2<\/jats:sub>]<jats:sub>2<\/jats:sub> (Cp*=1,2,3,4,5\u2010pentamethylcyclopentadienyl) as the metal precursor. Insight in the mechanism of the C\uf8ffH bond activation of phosphinines as well as in the regioselectivity of the reaction was obtained by time\u2010dependent <jats:sup>31<\/jats:sup>P{<jats:sup>1<\/jats:sup>H}\u2005NMR spectroscopy. At room temperature, 2,4,6\u2010triarylphosphinines instantaneously open the Ir\u2010dimer and coordinate in an \u03b7<jats:sup>1<\/jats:sup>\u2010fashion to the metal center. Upon heating, a dissociation step towards free ligand and an Ir\u2010acetate species is observed and proven to be a first\u2010order reaction with an activation energy of \u0394<jats:italic>E<\/jats:italic><jats:sub>A<\/jats:sub>=56.6\u2005kJ\u2009mol<jats:sup>\u22121<\/jats:sup> found for 2,4,6\u2010triphenylphosphinine. Electron\u2010donating substituents on the <jats:italic>ortho<\/jats:italic>\u2010phenyl groups of the phosphorus heterocycle facilitate the subsequent cyclometalation reaction, indicating an electrophilic C\uf8ffH activation mechanism. The cyclometalation reaction turned out to be very sensitive to steric effects as even small substituents can have a large effect on the regioselectivity of the reaction. The cyclometalated products were characterized by means of NMR spectroscopy and in several cases by single\u2010crystal X\u2010ray diffraction. Based on the observed trends during the mechanistic investigation, a concerted base\u2010assisted metalation\u2013deprotonation (CMD) mechanism, which is electrophilic in nature, is proposed.<\/jats:p>","DOI":"10.1002\/chem.201301693","type":"journal-article","created":{"date-parts":[[2013,8,9]],"date-time":"2013-08-09T07:58:01Z","timestamp":1376035081000},"page":"13087-13098","source":"Crossref","is-referenced-by-count":28,"title":["Cyclometalation of Aryl\u2010Substituted Phosphinines through C\uf8ffH\u2010Bond Activation: A Mechanistic Investigation"],"prefix":"10.1002","volume":"19","author":[{"given":"Leen E. 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