Cyclometalated Gold(III) Complexes: Synthesis, Reactivity, and Physicochemical Properties

Kumar, Roopender; Nevado, Cristina

doi:10.1002/anie.201607225

Cited by 167 publications

(135 citation statements)

References 178 publications

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“…It shows a triplet at −264 ppm corresponding to the fluorine atom in trans ‐position to the NCCH 3 ligand and a doublet at −296 ppm corresponding to the two fluorine atoms in cis ‐position. For [Au(CF 3 ) n F 4− n ] − , [AuF n Cl m (CF 3 ) 4− n − m ] − and cis ‐[Au(NHC)(Alkyl)F 2 ] the signal for the trans ‐positioned fluorido ligand is found at a chemical shift from −260 to −170 ppm which is in agreement with 1 . The intensity of the signals is as expected 2:1 (doublet : triplet).…”

Section: Resultssupporting

confidence: 65%

“…Gold chemistry is remarkable in catalysis, in part because of strong relativistic effects which can be linked to exceptional new reaction pathways . The vast majority of these investigations concentrate on Au I and sometimes Au III compounds that are based on gold chloride precursors as easy to handle materials . Hence, a lot of chloro organo gold compounds are known, but synthetic approaches for fluorido organo gold compounds are rare and either use a Cl/F exchange reaction as done by Sadighi et al., who synthesized the first fluorido gold(I) compound stabilized by an N‐heterocyclic carbene, or reaction pathways which involve an oxidation with XeF 2 .…”

Section: Introductionmentioning

confidence: 99%

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Taming the High Reactivity of Gold(III) Fluoride: Fluorido Gold(III) Complexes with N‐Based Ligands

Ellwanger

Steinhauer

Golz

et al. 2017

Chemistry A European J

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The synthesis of [NMe ][AuF ] and [NEt ][AuF ], as well as an improved one-pot synthesis of Cs[AuF ], is reported. The new [AuF ] salts were structurally characterized by single crystal X-ray diffraction, NMR spectroscopy, vibrational spectroscopy, and mass spectrometry. These salts are the first gold(III) fluoride salts that can be isolated in pure form and are convenient to be used in usual organic solvents for subsequent synthesis. The formation of molecular AuF complexes in solution is further reported, characterized as [F Au(NCCH )] at low temperature, as [F Au(py)] and a binuclear derivative which are stable at room temperature. The stability of these species in common organic solvents was investigated and they showed a satisfying stability.

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Section: Resultssupporting

confidence: 65%

Section: Introductionmentioning

confidence: 99%

Taming the High Reactivity of Gold(III) Fluoride: Fluorido Gold(III) Complexes with N‐Based Ligands

Ellwanger

Steinhauer

Golz

et al. 2017

Chemistry A European J

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“…The relativistic effects cause the contraction of 6s and 6p orbitals andt he expansion of 5d orbitals in Au I . [113][114][115][116] Therefore, progress in Au III catalysis could expand the overall scope of homogeneous Au catalysis. In fact, the soft Lewis acid nature and stable linear geometries of Au I complexesa re attributed to the strongr elativistic effects.…”

Section: Introductionmentioning

confidence: 99%

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

Nijamudheen

Datta

2019

Chemistry A European J

145

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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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“…Following in this line, B is not the only atom able to be incorporated to the oxazolone or imidazolone scaffolds. In particular, the incorporation of transition metals forming C,N‐cyclometallated derivatives in highly advantageous due to several reasons (Figure , right part) . This type of ligands provides exceptional thermodynamic stability to the resulting complexes and modifies the molecular orbital distribution, deactivating non‐radiative transitions centered in the metal orbitals.…”

Section: Introductionmentioning

confidence: 99%

Orthopalladation of GFP‐Like Fluorophores Through C–H Bond Activation: Scope and Photophysical Properties

et al. 2018

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The luminescence of oxazolones R1‐C6H4CH=CC(O)O‐CN(R2) (1a–1j) and imidazolones R1‐C6H4CH=CC(O)NR3CN(R2) (1k–1q) has been examined. The new GFP‐like imidazolones (GFP = Green Fluorescent Protein) (1k–1q) have been prepared by reaction of the oxazolones with amines H2NR3 and bis(trimethylsilyl)acetamide. The most intense fluorescence was found in push‐pull systems containing simultaneously strong electron‐donating and electron‐withdrawing substituents. The incorporation of the Pd atom into the molecular skeleton of oxazolones and imidazolones notably changes their luminescence. The reaction of oxazolones (1a–1j) and imidazolones (1k–1q) with Pd(OAc)2 (1:1 molar ratio) in carboxylic acids gives the dinuclear [Pd{R1‐C6H3CH=CC(O)OCN(R2)}(µ‐carboxylate)]2 (2a–2j) and [Pd{R1‐C6H3CH=CC(O)NR3CN(R2)}(µ‐carboxylate)]2 (2k–2q) through regioselective C–H bond activation of the ortho position of the respective 4‐arylidene rings. Complexes 2a–2q react with LiCl in MeOH to give the chloride‐bridge derivatives [Pd{R1‐C6H3CH=CC(O)OCN(R2)}(µ‐Cl)]2 (3a–3j) and [Pd{R1‐C6H3CH=CC(O)NR3CN(R2)}(µ‐Cl)]2 (3k–3q), which further react with Tl(acac) (acac = acetylacetonate) to give the mononuclear species [Pd(R1‐C6H3CH=CC(O)OCN(R2)(acac)] (4a–4j) and [Pd{R1‐C6H3CH=CC(O)NR3CN(R2)(acac)}] (4k–4q). Complexes 4o and 4q, having an orthopalladated push‐pull imidazolone, are strongly fluorescent, showing a notable increase of the quantum yield with respect to the free ligands 1o and 1q up of one order of magnitude.

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Cyclometalated Gold(III) Complexes: Synthesis, Reactivity, and Physicochemical Properties

Cited by 167 publications

References 178 publications

Taming the High Reactivity of Gold(III) Fluoride: Fluorido Gold(III) Complexes with N‐Based Ligands

Taming the High Reactivity of Gold(III) Fluoride: Fluorido Gold(III) Complexes with N‐Based Ligands

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

Orthopalladation of GFP‐Like Fluorophores Through C–H Bond Activation: Scope and Photophysical Properties

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