Expedient Syntheses of Neutral and Cationic Au(I)–NHC Complexes

Veenboer, Richard M. P.; Gasperini, Danila; Nahra, Fady; Cordes, David B.; Slawin, Alexandra M. Z.; Cazin, Catherine S. J.; Nolan, Steven P.

doi:10.1021/acs.organomet.7b00622

Cited by 22 publications

(27 citation statements)

References 61 publications

(88 reference statements)

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“…FTIR‐ATR of neat 4 shows signals (ν C≡N 2332, 2306 cm −1 ) which are higher than those for NCCH 3 (ν C≡N 2254, 2293 cm −1 ) due to the change in the electronic configuration of the acetonitrile upon complexation . This is expected since the electron donation from the lone pair of the NCCH 3 to the gold center removes weakly antibonding electrons from the σ orbital at the CN bond upon coordination, and therefore strengthening it and increasing its stretching frequency (ν C≡N ) …”

Section: Resultsmentioning

confidence: 96%

“…With the neutral NHC−Au(I) complexes in hand, we aimed on the synthesis of highly electron‐deficient cationic complexes by anion metathesis using weakly coordinating counter anions. We envisaged hexafluoroantimonate (SbF 6 − ) and triflimidate (NTf 2 − ), as suitable moieties for the synthesis of cationic NHC−Au(I) complexes . To this end, the treatment of the gold(I) chloride complexes with 1 equivalent of either AgSbF 6 or AgNTf 2 was attempted (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

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Gold(I) Complexes with Eight‐Membered NHC Ligands: Synthesis, Structures and Catalytic Activity

et al. 2020

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A series of expanded‐ring NHC gold complexes of the formula (NaphtDHD−Ar)Au−X (NaphtDHD=4,5‐dihydro‐1H‐naphtho[1,8‐ef][1,3]diazocin‐3(2H)‐ylidene; Ar: Mes=2,4,6‐trimethylphenyl, Dipp=2,6‐diisopropylphenyl or Xyl=2,6‐dimethylphenyl; X=Cl, NCCH3, NTf2) have been synthesized, including the first gold(I) triflimidate complex (5) stabilized by an eight‐membered NHC ligand. The new organogold compounds have been characterized by mass spectrometry, IR spectroscopy, and 1H and 13C NMR spectroscopy. The structural geometries of 3 b–c and 5 have been unequivocally established by crystallographic analysis revealing broad N‐C‐N angles (>121°) and high buried volume values (46–54%). The first catalytic studies were carried out on the cycloisomerization of 1,6‐enynes, obtaining full conversions (0.5 mol% catalyst loading) and excellent endo/exo selectivity (up to 99:1), and on the gold‐catalyzed phenol synthesis. Lastly, the (NaphtDHD‐Dipp)Au+ NTf2− species was subjected to a kinetic experiment in the cyclization of a N‐propargyl carboxamide to evaluate the efficiency of the pre‐formed catalyst (5) and the in situ activated gold complex (3 b+AgNTf2).

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Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

Gold(I) Complexes with Eight‐Membered NHC Ligands: Synthesis, Structures and Catalytic Activity

et al. 2020

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“…[53][54][55][56] Compared with the advances in heterogeneous goldc atalysis, the field of homogeneous gold catalysis startedt og row only in the first decade of the 21st century.O ver the past two decades, homogeneousg old catalysis has emerged as an eminent synthetic methodology.T he progress in the syntheses and applications of Au catalysts, related reaction mechanisms, and the future prospects of traditional Au I -catalyzed reactions have been reviewed by the groups of Hashmi, [57][58][59][60][61][62] Fürstner, [63,64] To ste, [65] Echavarren, [66][67][68] and others. [92,93,102,[94][95][96][97][98][99][100][101] Some reactions are best catalyzed when multiple Au centers are available to activate the reactants and/or intermediates. Being ah eavy atom with a5 d 10 6s 1 electronic configuration, the relativistic effects strongly affect the dynamics of the valence electrons of Au.…”

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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“…The Au(I) complexes that can exist as mononuclear and polynuclear complexes with one or more NHC moieties per ligand can generate a strong linear coordination bond between Au(I) and carbene carbon to facilitate the formation of Au(I)–NHC complexes. The ionic structure of Au(I)–NHC complexes can be either as singly coordinated halide as neutral complexes in the form of [XAu(I)(NHC)] (with X = Cl, Br, I) or as non‐coordinated cations like [Au(I)(NHC) 2 ]X (X = PF 6 − , BF 4 − , Cl − , Br − , I − ) which subsequently balance with the charges of anions present in the lattice . As regards synthesis protocols, Au(I)–NHC complexes can be prepared through a few common methods as reported before .…”

Section: Introductionmentioning

confidence: 99%

Coinage metal complexes of N‐heterocyclic carbene bearing nitrile functionalization: Synthesis and photophysical properties

Hussaini

Haque

et al. 2019

Applied Organom Chemis

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A new series of N-heterocyclic carbene (NHC) ligand precursors (1 and 2) with their [Ag(I)(NHC) 2 ]PF 6 complexes (3 and 4) and [ClAu(I)(NHC)] complexes (5 and 6) are reported. Complexes 5 and 6 were synthesized via transmetalation reaction using either 3 or 4 and AuCl(SMe 2 ) as reactants, respectively. All the synthesized compounds were fully characterized using elemental analyses and Fourier transform infrared, 1 H NMR and 13 C NMR spectroscopies. In the crystal structures of 3, 5 and 6, the Ag(I) and Au(I) ions are in a linear geometry. The entire structure of 3 is stabilized by significant π-π interactions, while the structures of 5 and 6 are stabilized with the presence of aurophilic interactions between the adjacent Au(I) ions as well as CH-π or π-π interactions. From photoluminescence studies, complexes 5 and 6 show dual-emission characteristics. The higher-energy fluorescence originates from 1 XLCT mixed with 1 MLCT, while the lower-energy phosphorescence is ascribed to 3 XLCT and 3 MLCT with small contribution of 3 ILCT, as evidenced by density functional theory (DFT) and time-dependent DFT calculations of the modelled molecules.

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Expedient Syntheses of Neutral and Cationic Au(I)–NHC Complexes

Abstract: ABSTRACT:The synthesis and isolation of gold (I)

Cited by 22 publications

References 61 publications

Gold(I) Complexes with Eight‐Membered NHC Ligands: Synthesis, Structures and Catalytic Activity

Gold(I) Complexes with Eight‐Membered NHC Ligands: Synthesis, Structures and Catalytic Activity

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

Coinage metal complexes of N‐heterocyclic carbene bearing nitrile functionalization: Synthesis and photophysical properties

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