Photoinitiated Reactions of Haloperfluorocarbons with Gold(I) Organometallic Complexes: Perfluoroalkyl Gold(I) and Gold(III) Complexes

Abstract

The study of perfluoroalkyl metal complexesi sk ey to understand and improvem etal-promoted perfluoroalkylation reactions. Herein, we report the synthesis of the first gold complexes with primaryo rs econdary perfluoroalkyl ligands by photoinitiated reactions between Au I organometallic complexes and iodoperfluoroalkanes.

Recent Advances in Gold(III) Chemistry: Structure, Bonding, Reactivity, and Role in Homogeneous Catalysis

“…Oxidation with I 2 gave the Au(III) trans-diiodide which was stable only at very low temperatures and underwent thermal reductive elimination of CF 3 I. In the case of the other halides, trans-dihalide Au(III) trifluoromethyl complexes 157 are thermally stable but reductively eliminate CF 3 Br and CF 3 Cl when exposed to UV light (Scheme 52).Photoinitiated reductive elimination from perfluoroalkyl Au(III) complexes was investigated by Portuguès et al323 In line with the previous results on trifluoromethyl derivatives, perfluoroalkyl iodides were found to oxidatively add to LAuR complexes (L = PPh 3 , IPr; R = Me, Mes, alkynyl) under irradiation at 402 nm and afforded Au(III) complexes with variable stability. In the case of L Irradiation in the presence of radical traps revealed that the decomposition follows a radical mechanism, in analogy to what was proposed for the photoinitiatied oxidative addition (see Section 3.1.3).…”

Gold Complexes with Difunctional Perfluoroalkyl Chains: Quantifying the Energy of Aurophilic Interactions in Flexible Open‐Chain Complexes

“…In contrast, complexes containing longer perfluoroalkyl chains have been much less explored. [9][10][11][12][13][14][15][16][17][18] Particularly, complexes containing difunctional perfluoroalkyl chains ( Figure 1) have received very little attention. Thus, a few binuclear complexes with bridging (CF 2 ) 2 chains have been prepared by insertion of C 2 F 4 into metal-metal bonds (A) [19][20][21][22] or by reaction of C 2 F 4 with low-oxidation-state metal complexes (B, C).…”

“…The sluggish reactions observed in the dark or in the presence of TEMPO (Supporting Information) suggest a pho-toinitiated radical mechanism analogous to that proposed for the reactions of LAuMe with IC n F 2n+1 . [18] It is noteworthy that, whereas the Au I complexes LAu( n C 4 F 9 ) (L = PPh 3 or IPr) are unreactive toward I n C 4 F 9 , [18] complexes LAu(CF 2 ) n I undergo intramolecular oxidative addition when n is 4, but not when n is 6 or 8. Since the reaction of 2 equivalents of Me 3 PAuMe with I(CF 2 ) 4 I gave a complex mixture where the expected binuclear complex 1 h was a minor component, we synthesized it by a phosphine substitution reaction on 1 a (Scheme 1).…”

Gold Complexes with Difunctional Perfluoroalkyl Chains: Quantifying the Energy of Aurophilic Interactions in Flexible Open‐Chain Complexes

“…The sluggish reactions observed in the dark or in the presence of TEMPO (Supporting Information) suggest a photoinitiated radical mechanism analogous to that proposed for the reactions of LAuMe with IC n F 2 n +1 . It is noteworthy that, whereas the Au I complexes LAu( n C 4 F 9 ) (L=PPh 3 or IPr) are unreactive toward I n C 4 F 9 , complexes LAu(CF 2 ) n I undergo intramolecular oxidative addition when n is 4, but not when n is 6 or 8. Since the reaction of 2 equivalents of Me 3 PAuMe with I(CF 2 ) 4 I gave a complex mixture where the expected binuclear complex 1 h was a minor component, we synthesized it by a phosphine substitution reaction on 1 a (Scheme ).…”

“…Notable progress toward this target has been made for metal trifluoromethyl complexes. In contrast, complexes containing longer perfluoroalkyl chains have been much less explored …”