Synthesis of gold-(<scp>I</scp>) and -(<scp>III</scp>) complexes with carbonyl-stabilized phosphorus ylides. Crystal structure of [{Au(PPh3)}2{µ-C(PPh3)CO2Et}]ClO4

Vicente, José; Chicote, Mariá‐Teresa; Cayuelas, José A.; Fernández‐Baeza, Juan; Jones, Peter G.; Sheldrick, George M.; Espinet, Pablo

doi:10.1039/dt9850001163

Cited by 89 publications

(70 citation statements)

References 5 publications

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“…Examples of dinuclear complexes with carbon donor ligands bridging the two gold centers connected through aurophilic interactions include cyclopentadienyl [169] dicyanomethane [170], cyano(phenylthiolato)methylidene (Figure 2.36a), nitro (phenylsulfonyl)methylidene [171], 2,3,6-trifluorophenyl [172], ethoxycarbonyl-(triphenylphosphoranylidene)-methyl [173], (2-pyridyl)-tri-p-tolylphosphinemethylene [174], triphenylphosphonio(2-pyridyl)methylene [175], bis(diphenylphoshino) methylidene (Figure 2.36b) [176] [179]. 1,2-bis(phenylene)ethane coordinates two gold atoms connected through aurophilic interactions to one carbon or each phenyl fragment [180].…”

Section: Complexes With Bridging Monodentate Ligandsmentioning

confidence: 99%

Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

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This chapter focuses mainly on closed shell gold(I) atoms which are found to feel attraction among themselves. This attraction is able to modify expected geometries or support one-, two-or three-dimensional arrays and also leads to interesting properties. Closed shell metal cations are expected to repel each other. Nevertheless, an important number of examples containing [d 8 -d 10 -s 2 ] interactions are known. Particularly strong evidence has been accumulated on the attraction between two or more d 10 shells. In the case of gold(I) such attraction between two or more monovalent gold(I) ions in compounds has been observed structurally for a long time. In these situations the gold centers approach each other to a distance of between 2.7 and 3.3 Å. This range includes the distance between gold atoms in gold metal and approaches, or even overlaps with the range of distances found in the few real Au-Au single bonds. Schmidbaur coined the name aurophilic attraction in 1990 and defined it as the unprecedented affinity between gold atoms even with closed-shell electronic configurations and equivalent electrical charges [1]. Since that moment, aurophilicity has become one of the hot topics in gold chemistry, at first with the aim of understanding such interaction, more recently because of the observation that it may play an important role in interesting properties, thus understanding and modulating aurophilic interactions could help to govern these properties, which include the optical behavior. Although different origins are possible for the luminescent emissions of coordination complexes, such as intraligand transitions (ILT), ligand to metal or metal to ligand charge transfer transitions (LMCT, MLCT) and metal centered (MCT) transitions, in many luminescent gold complexes the emissions have been related to the presence of aurophilic interactions.Information about aurophilicity and chemical situations in which it is observed may be found in different works that may be classified as those which analyse closed shell interactions in general [2], those focused on aurophilicity [1,3], and others which analyze the role of these interactions in coordination [4] and organometallic gold Modern Supramolecular Gold Chemistry: Gold-Metal Interactions and Applications. Edited by Antonio Laguna

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Section: Complexes With Bridging Monodentate Ligandsmentioning

confidence: 99%

Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

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“…Two gold atoms at a common non-arene carbon atom were soon detected also in ylidic species. No comment would be necessary here, were it not that the Au-C-Au angles are found to be smaller than the tetrahedral value [82][83][84]. Equally unexpected were the readiness of formation of triauro-oxonium, -sulfonium, and -selenonium salts, and the molecular structures of these products [76a,85-89]: in all cases, steep pyramids [E(AuL)3]+ with E = 0, S, Se, and short Au•••Au contacts were detected, and these units are further dimerized to allow for even more Au•••Au intercationic interactions.…”

Section: Single-atom Bridged Polynuclear Gold Complexesmentioning

confidence: 99%

The fascinating implications of new results in gold chemistry

1990

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“…The reaction of (phosphine)gold(I) halides with ylides of the type R 0 2 CDPR 00 3 proceeds in two steps: Initial displacement of halide gives an isolable monoylide species, which can be transformed into a bis(ylide)gold(I) complex if an excess of ylide is employed (Scheme 7) 15 . In some instances, however, the reaction produces the bis(ylide) species directly, regardless of the relative ratios of gold (I) Carbonyl-stabilized phosphorus ylides are less nucleophilic and hence do not react with (phosphine)gold(I) halides, but their gold(I) complexes can be generated from precursors such as [Au(acac)(PPh 3 )] or [AuCl(SC 4 H 8 )] by reaction with phosphonium salts and ylides, respectively, and again both mono-and bis(ylide) complexes have been obtained (equation 48 and Scheme 8) 206,207 . The ylide carbon atoms in these complexes are centres of chirality, but no stereospecificity was observed in the coordination process and racemic mixtures are formed throughout.…”

Section: Mononuclear Ylide Complexesmentioning

confidence: 99%

“…This approach is exemplified by complexes of the general types [AuX 3 (ylide)] 216 , trans-[Au(C 6 F 5 )X 2 (ylide)] 216 and trans-[AuX 2 (ylide) 2 ]ClO 4 (X D Cl, Br) 206,207 , some of which may be further converted into the related iodo or thiocyanato complexes by reaction with potassium iodide or potassium thiocyanate 216 . Additionally, a few methods for the direct synthesis of gold(III) ylide complexes have been described.…”

Section: Mononuclear Ylide Complexesmentioning

confidence: 99%