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Reactions proceed in dichloromethane solvent at room temperature. Identical C\u2212H functionalization conditions and stoichiometries are employed for generality and convenience. Selectivities for C\u2212H insertions are higher for compounds possessing stronger electron\u2010withdrawing substituents. Preliminary mechanistic studies point to a mechanism involving a pre\u2010equilibrium forming a \u201csandwich\u201d\u2010diimine copper\u2010CF<jats:sub>3<\/jats:sub>CHN<jats:sub>2<\/jats:sub> complex followed by rate\u2010determining loss of nitrogen affording the reactive copper carbene. It reacts with trifluoromethyldiazomethane about 6.5\u2005times faster than with 1\u2010fluoroadamantane explaining the need for slow addition of the diazo compound.<\/jats:p>","DOI":"10.1002\/chem.202301672","type":"journal-article","created":{"date-parts":[[2023,6,2]],"date-time":"2023-06-02T12:09:25Z","timestamp":1685707765000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["\u201cSandwich\u201d Diimine\u2010Copper Catalyzed Trifluoroethylation and Pentafluoropropylation of Unactivated C(sp<sup>3<\/sup>)\u2212H Bonds by Carbene Insertion"],"prefix":"10.1002","volume":"29","author":[{"given":"Thanh V.","family":"Le","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Houston  3585 Cullen Blvd Houston TX USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Irvin","family":"Romero","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of 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