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Herein, we report the synthesis of the first gold complexes with primary or secondary perfluoroalkyl ligands by photoinitiated reactions between Au<jats:sup>I<\/jats:sup> organometallic complexes and iodoperfluoroalkanes. Complexes of the types LAuR<jats:sub>F<\/jats:sub> (L=PPh<jats:sub>3<\/jats:sub> or <jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2010bis(2,6\u2010diisopropylphenyl)imidazol\u20102\u2010ylidene; R<jats:sub>F<\/jats:sub>=<jats:italic>n<\/jats:italic>\u2010C<jats:sub>4<\/jats:sub>F<jats:sub>9<\/jats:sub>, <jats:italic>n<\/jats:italic>\u2010C<jats:sub>6<\/jats:sub>F<jats:sub>13<\/jats:sub>, <jats:italic>i<\/jats:italic>\u2010C<jats:sub>3<\/jats:sub>F<jats:sub>7<\/jats:sub>, <jats:italic>c<\/jats:italic>\u2010C<jats:sub>6<\/jats:sub>F<jats:sub>11<\/jats:sub>) and [Au(R<jats:sub>F<\/jats:sub>)(Ar)I(PPh<jats:sub>3<\/jats:sub>)] (Ar=2,4,6\u2010trimethylphenyl) have been isolated and characterized. Alkynes R<jats:sub>F<\/jats:sub>C\u2261CR were formed by reaction of Ph<jats:sub>3<\/jats:sub>PAuC\u2261CR (R=Ph, <jats:italic>n<\/jats:italic>Hex) with IR<jats:sub>F<\/jats:sub> (R<jats:sub>F<\/jats:sub>=<jats:italic>n<\/jats:italic>\u2010C<jats:sub>4<\/jats:sub>F<jats:sub>9<\/jats:sub>, <jats:italic>i<\/jats:italic>\u2010C<jats:sub>3<\/jats:sub>F<jats:sub>7<\/jats:sub>). According to the evidences obtained, this transformation undergoes through a photoinitiated radical mechanism. Au<jats:sup>III<\/jats:sup> complexes [Au(<jats:italic>n<\/jats:italic>\u2010C<jats:sub>4<\/jats:sub>F<jats:sub>9<\/jats:sub>)(X)(Y)L] (X=Y=Cl, Br, I, Me; X=Me, Y=I) have been prepared or in situ generated, and their thermal or photochemical decomposition reactions have been studied.<\/jats:p>","DOI":"10.1002\/chem.201903058","type":"journal-article","created":{"date-parts":[[2019,9,4]],"date-time":"2019-09-04T12:59:32Z","timestamp":1567601972000},"page":"15535-15547","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Photoinitiated Reactions of Haloperfluorocarbons with Gold(I) Organometallic Complexes: Perfluoroalkyl Gold(I) and Gold(III) Complexes"],"prefix":"10.1002","volume":"25","author":[{"given":"Alejandro","family":"Portugu\u00e9s","sequence":"first","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Facultad de Qu\u00edmica Universidad de Murcia  Campus de Espinardo 30100 Murcia Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Inmaculada","family":"L\u00f3pez\u2010Garc\u00eda","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Facultad de Qu\u00edmica Universidad de Murcia  Campus de Espinardo 30100 Murcia Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Javier","family":"Jim\u00e9nez\u2010Bernad","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Facultad de Qu\u00edmica Universidad de Murcia  Campus de Espinardo 30100 Murcia Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Delia","family":"Bautista","sequence":"additional","affiliation":[{"name":"ACTI. 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