Thermal versus Photochemical Reductive Elimination of Aryl Chlorides from NHC–Gold Complexes

Ghidiu, Michael; Pistner, Allen J.; Yap, Glenn P. A.; Lutterman, Daniel A.; Rosenthal, Joel

doi:10.1021/om400701f

Cited by 36 publications

(36 citation statements)

References 38 publications

(45 reference statements)

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“…to give an Au II intermediate that was further reduced . In contrast, the in situ formation of dichlorine is characteristic of a nonradical reductive elimination mechanism, in agreement with Kochi's proposed mechanism (Scheme , see the ionic pathway leading to + Au III Cl 2 + Cl − ), or a direct cis ‐elimination process (Scheme , see direct reductive elimination leading to Au I Cl) ,. Therefore, both radical and nonradical photoreduction pathways appear to operate during the reduction of gold(III) chloride thioether complexes.…”

Section: Resultssupporting

confidence: 76%

Photoreduction of Thioether Gold(III) Complexes: Mechanistic Insight and Homogeneous Catalysis

Cao

Bassani

Bibal

2018

Chemistry A European J

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Complexes formed between AuCl3 and thioether ligands underwent a photoinduced reductive elimination under homogeneous conditions in dichloromethane and toluene solutions to afford the corresponding AuI complexes. All the gold(III) complexes were rapidly reduced to the gold(I) chloride complexes under 365 nm irradiation or ambient light while being thermally stable below 55 °C. The mechanism of photoreduction through Cl2 elimination is discussed based on a kinetic study and the chemical trapping of chlorine species: Cl2, radical Cl., and possibly Cl+. The catalytic activities of the gold(III) chloride complexes and the corresponding gold(I) complexes obtained by in situ reduction were evaluated in the cyclization of N‐propargylic amides to oxazoles. The merits of such photoreducible complexes in homogeneous gold catalysis are illustrated by a cascade reaction catalyzed by thioether gold complexes that affords a 4H‐quinolizin‐4‐one in high yields.

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Section: Resultssupporting

confidence: 76%

Photoreduction of Thioether Gold(III) Complexes: Mechanistic Insight and Homogeneous Catalysis

Cao

Bassani

Bibal

2018

Chemistry A European J

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“…[336] For Ar = C 6 H 5 ,afast thermal C(sp 2 )ÀCl reductive elimination is observed, whereas for Ar = C 6 F 5 no reductive elimination is found even at an elevated temperature. [336] For Ar = C 6 H 5 ,afast thermal C(sp 2 )ÀCl reductive elimination is observed, whereas for Ar = C 6 F 5 no reductive elimination is found even at an elevated temperature.…”

Section: Carbon-heteroatom Bond-forming Reductive Elimination From Gomentioning

confidence: 94%

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Nijamudheen

Datta

2019

Chemistry A European J

136

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Transition-metal-catalyzed cross-couplingr eactions are central to many organic synthesis methodologies. Traditionally,P d, Ni, Cu, and Fe catalysts are used to promote these reactions. Recently,m any studies have showedt hat both homogeneous and heterogeneous Au catalysts can be used for activating selective cross-coupling reactions.H ere, an overview of the past studies, current trends, andf uture directions in the field of gold-catalyzed coupling reactions is presented.D esign strategiest oa ccomplish selective homocoupling and cross-coupling reactions under both homogeneous and heterogeneous conditions, computational and ex-perimental mechanistic studies, and their applicationsi nd iverse fields are critically reviewed. Specific topics covered are:o xidant-assisted and oxidant-free reactions;s train-assisted reactions;d ual Au and photoredoxc atalysis;b imetallic synergistic reactions;m echanismso fr eductivee limination processes;e nzyme-mimicking Au chemistry;c lustera nd surface reactions;a nd plasmonic catalysis. In the relevant sections, theoretical and computational studies of Au I /Au III chemistry are discussed and the predictionsf rom the calculationsa re compared with the experimental observations to derive useful design strategies.A. Nijamudheen earnedh is PhD from IACS, Kolkata,i n2 015. Currently,h ei sapostdoctoral researcher atF loridaS tate University.H is researchi nterests are in computational catalysis, solar energym aterials, and beyond Li-ion battery technologies.Ayan Dattai sc urrently aP rofessor at IACS, Kolkata.H is research interests include theoretical and computational studieso ft ransitionmetal-catalyzed reactions,o pto-electronic properties of organic and solid-statem aterials, and the design of renewableenergymaterials. He has won several awards including the DST-SERB Distinguished Investigator Award (DIA) in 2019.

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“…Complex 2 also photodecomposed (380 nm) to 4 at room temperature or at 77 K. (A gold(III) complex was recently reported to undergo photolytic reductive elimination of aryl chloride. 31 ) In addition to its photochemical reactivity, 1 is photoluminescent in MeTHF glass at 77 K. Irradiation at 380 nm gives visible salmon-pink emission (λ max = 620 nm). The emission lifetime (38 μs) and intensity decrease as the photolysis progresses indicate that emission is from a triplet excited state of a species that is photodecaying; in other words, the emission is from a triplet of 1.…”

mentioning

confidence: 99%

Hydroxo Radicals, C–H Activation, and Pt–C Bond Formation from 77 K Photolysis of a Platinum(IV) Hydroxo Complex

Wickramasinghe

Sharp

2014

Inorg. Chem.

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Photolysis (380 nm) of trans,cis-Pt(PEt3)2(Cl)2(OH)(4-tft) (4-tft = 4-trifluoromethylphenyl) at 77 K in 2-methyltetrahydrofuran gives triplet emission, platinum(III), and a hydroxo radical. Benzyl radical emission is observed in toluene from the reaction of a portion of the OH radicals with toluene. Warming the photolyzed solutions gives platinacycle trans-Pt(CH2CH2PEt2)(PEt3)(Cl)2(4-tft) by hydrogen-atom abstraction from a PEt3 ligand and trans-Pt(PEt3)2(Cl)(4-tft) from net HOCl photoelimination. The platinacycle undergoes thermal reductive elimination at 298 K or photolytic reductive elimination, even at 77 K.

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Thermal versus Photochemical Reductive Elimination of Aryl Chlorides from NHC–Gold Complexes

Cited by 36 publications

References 38 publications

Photoreduction of Thioether Gold(III) Complexes: Mechanistic Insight and Homogeneous Catalysis

Photoreduction of Thioether Gold(III) Complexes: Mechanistic Insight and Homogeneous Catalysis

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Hydroxo Radicals, C–H Activation, and Pt–C Bond Formation from 77 K Photolysis of a Platinum(IV) Hydroxo Complex

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