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A common method to introduce the trifluoromethyl group employs the Ruppert\u2013Prakash reagent, that is, Si(CH<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>CF<jats:sub>3<\/jats:sub>, together with a copper(I) halide. We have applied this method to the trifluoromethylation of aromatic alkynes and used electrospray\u2010ionization mass spectrometry to investigate the mechanism of these reactions in tetrahydrofuran, dichloromethane, and acetonitrile as well as with and without added 1,10\u2010phenanthroline. In the absence of the alkyne component, the homoleptic ate complexes [Cu(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> and [Cu(CF<jats:sub>3<\/jats:sub>)<jats:sub>4<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> were observed. In the presence of the alkynes RH, the heteroleptic complexes [Cu(CF<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>R]<jats:sup>\u2212<\/jats:sup> were detected as well. Upon gas\u2010phase fragmentation, these key intermediates released the cross\u2010coupling products R\u2212CF<jats:sub>3<\/jats:sub> with perfect selectivity. Apparently, the [Cu(CF<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>R]<jats:sup>\u2212<\/jats:sup> complexes did not originate from homoleptic cuprate anions, but from unobservable neutral precursors. The present results moreover point to the involvement of oxygen as the oxidizing agent.<\/jats:p>","DOI":"10.1002\/chem.201601261","type":"journal-article","created":{"date-parts":[[2016,7,7]],"date-time":"2016-07-07T04:50:05Z","timestamp":1467867005000},"page":"11310-11316","source":"Crossref","is-referenced-by-count":19,"title":["The Role of Ate Complexes in the Copper\u2010Mediated Trifluoromethylation of Alkynes"],"prefix":"10.1002","volume":"22","author":[{"given":"Sebastian","family":"Weske","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Organische und Biomolekulare Chemie Georg-August-Universit\u00e4t G\u00f6ttingen  Tammanstra\u00dfe 2 37077 G\u00f6ttingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ramona","family":"Schoop","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Organische und Biomolekulare Chemie Georg-August-Universit\u00e4t G\u00f6ttingen  Tammanstra\u00dfe 2 37077 G\u00f6ttingen 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