Constrained Digold(I) Diaryls: Syntheses, Crystal Structures, and Photophysics

Partyka, David V.; Teets, Thomas S.; Zeller, Mat­thias; Updegraff, James B.; Hunter, Allen D.; Gray, Thomas

doi:10.1002/chem.201101891

Cited by 41 publications

(20 citation statements)

References 41 publications

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“…In 2011, gold complexes with these ligands were prepared in situ and used for the domino cyclization/nucleophile addition reactions of enynes in the presence of water, methanol, and electron-rich aromatic derivatives. [10] The structural differences between those complexes were, however, relatively large -in contrast to the compounds examined in this study. [9] We also note a recent study dealing with the photophysical properties of constrained diaryldigold(I) compounds.…”

Section: Introductioncontrasting

confidence: 57%

[2.2]Paracyclophanediyldiphosphane Complexes of Gold

et al. 2012

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We have prepared digold(I) complexes with the rigid-backbone diphosphane ligands PhanePhos, xyl-PhanePhos, and Ph 2 -GemPhos. All complexes were characterized by singlecrystal X-ray diffraction, NMR, IR, Raman, and photoluminescence (PL) spectroscopy. [PhanePhos(AuCl) 2 ] and [Gem-Phos(AuCl) 2 ] show a very similar ligand scaffold, but different (aurophilic vs. nonaurophilic) intramolecular Au-Au distances. Absorption and PL spectra of both compounds are quite similar. Theoretical investigations reveal that the excited states are of different character (i.e., influenced by the Au-Au contacts). The respective transition energies, however, lie close to each other, thus resulting in similar experi-

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Section: Introductioncontrasting

confidence: 57%

[2.2]Paracyclophanediyldiphosphane Complexes of Gold

et al. 2012

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“…A more sterically demanding boronic acid also led to high yield of the corresponding gold complex under these conditions ( 2 c ). Compound 2 d , which was shown to possess interesting physical properties, was obtained in an excellent yield . Boronic acids bearing electron‐withdrawing groups at various positions also led to the desired gold–aryl complexes in high yields ( 2 e , 2 f and 2 g ).…”

Section: Resultsmentioning

confidence: 97%

Simple Synthetic Routes to N‐Heterocyclic Carbene Gold(I)–Aryl Complexes: Expanded Scope and Reactivity

Tzouras

Saab

Janssens

et al. 2020

Chemistry A European J

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Thediscoveryofsustainable and scalablesynthetic protocols leading to gold-arylcompounds bearing N-heterocyclic carbene (NHC) ligandss parkeda ni nvestigationo f their reactivitya nd potential utility as organometallic synthons. The use of am ild base andg reen solvents provide access to these compounds, startingf rom widely available boronic acids and various [Au(NHC)Cl] complexes, with reactions taking place under air,a tr oom temperature and lead-ing to high yields with unprecedented ease. One compound, (N,N'-bis[2,6-(di-isopropyl)phenyl]imidazol-2-ylidene)(4-methoxyphenyl)gold, ([Au(IPr)(4-MeOC 6 H 4 )]), was synthesized on am ultigrams cale and used to gauge the reactivity of this class of compounds towards CÀH/NÀHb onds and with various acids, revealings imple pathways to gold-based species that possess attractive properties as materials, reagents and/ or catalysts. Results and DiscussionOur initial approachq uestioned whether the transmetallation reaction between [Au(IPr)Cl] (1)a nd an equimolar amount of phenylboronic acid was feasible in technical grade acetonei n the presence of K 2 CO 3 (entry 1, Ta ble 1). This initial hypothesis is based on our recent work using aw eak inorganic base to [a] N.

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“…The vibronic emission and the large Stokes shift suggest phosphorescence from a triplet excited state, as observed in other gold(I) organometallics. [25][26][27][28][29] Density functional theory calculations have been applied to models of 1, 6, and 11, where PMe 3 ligands replace PPh 3 for computational simplicity. These model complexes are 1', 6' and 11', respectively.…”

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confidence: 99%

“…These results suggest some gold participation in the excited states of geminally diaurated aryls, whereas phosphorescence of normal gold(I) aryls and alkynyls is ligand-centered. [25][26][27][28][29][31][32][33] The available crystal structures suggest disrupted aromaticity, as do the optimized geometries. Perturbations of carbon-carbon bond lengths decrease with distance from the dimetallation site.…”

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confidence: 99%

Geminally Diaurated Gold(I) Aryls from Boronic Acids

et al. 2012

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Gold catalysts and catalyst precursors have commanded attention for more than a decade. Several reviews [1][2][3][4][5][6][7][8] highlight the utility of gold in organic transformations. Recent efforts have succeeded in isolating putative intermediates of alkene and alkyne transformations. In 2008, Hammond and coworkers generated aurated g-lactone complexes from allenes. [9] Later, Bertrand, Hashmi, and their respective coworkers independently reported vinylgold(I) species derived from alkynes. [10] GagnØ and co-workers first implicated geminally diaurated species as resting states in catalytic cycles of gold by reacting vinylgold(I) species with one equivalent of gold(I) cation. [11] Fürstner and co-workers later showed that transmetalation from boron using the Gagosz complex [12] ([Ph 3 PAu]NTf 2 , Tf= trifluoromethanesulfonyl) gave only geminally diaurated species regardless of the number of equivalents used. [13] Such species are not recent discoveries. Work by Nesmeyanov and co-workers in the 1970s produced the first geminally diaurated aromatic ring systems, bis(triphenylphosphine)gold(I) complexes of ferrocene. [14] The work was soon expanded to include adducts of heteroarenes. [15] Schmidbaur and co-workers have reported geminally diaurated diketones and disulfones, [16] as well as arenes, although with lithiated reagents. [17] Most recently, Hashizume et al. generated a gemdiaurated 2-naphthyl species by protonation with perchloric acid of mono-gold complexes, with subsequent capture of the released cationic gold fragment. [18] In contrast to the recent development of diaurated vinyl complexes, the frontier of arene gem-diauration remains relatively quiet. A very recent report by GagnØ and co-workers disclosed a preparation of several diaurated species from parent monoaurated arenes. [19] Such species deserve further investigation.Due to the isolobality of the proton and the LAu + fragment (L = phosphine, carbene, and others), [20,21] diaurated arenes are analogues of Wheland intermediates in electrophilic aromatic substitutions (Scheme 1). However, future studies would benefit from mild methods of generating these complexes. All established routes require hazardous reagents, or they entail the loss of one half equivalent of aryl liganda costly issue in the case of value-added organic ligands. Here, we disclose syntheses of geminally diaurated arenes from arylboronic acids [22] without the need for activating silver salts, Brønsted acids, or Grignard reagents. The reactions are mild, quick, and high-yielding. In most cases the isolated solids are pure. No air-or moisture-free techniques were employed. All products are fully characterized by 1 H and 31 P NMR spectroscopy and elemental analysis, unless otherwise noted; 13 C NMR data are not reported because attempts to detect the bridging, ipso-carbon were unsuccessful. [23] For several of the products, crystals suitable for X-ray diffraction analysis were grown.Reaction of one-half equivalent of arylboronic acid with [Ph 3 PAu]NTf 2 in diethyl ether led t...

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Constrained Digold(I) Diaryls: Syntheses, Crystal Structures, and Photophysics

Cited by 41 publications

References 41 publications

[2.2]Paracyclophanediyldiphosphane Complexes of Gold

[2.2]Paracyclophanediyldiphosphane Complexes of Gold

Simple Synthetic Routes to N‐Heterocyclic Carbene Gold(I)–Aryl Complexes: Expanded Scope and Reactivity

Geminally Diaurated Gold(I) Aryls from Boronic Acids

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