Silver and Gold

Gimeno, M. Concepción; Laguna, Antonio

doi:10.1016/b0-08-043748-6/05122-7

Cited by 81 publications

(64 citation statements)

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“…The reaction of FcCH 2 NMe 2 with 6-amino-2-picoline (NH 2 pyMe) in acetic acid gives the ferrocene ligand FcCH 2 NHpyMe (1) [Equation (1)]. A closely related ferrocene derivative, FcCONHpyMe, has previously been reported and the effect of protonation on the spectroscopic and redox properties was studied.…”

Section: Synthesis Of the Complexesmentioning

confidence: 99%

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The Role of Secondary Interactions in Group 11 Metal Complexes Containing the Ferrocene Ligand FcCH₂NHpyMe in Supramolecular Structures

et al. 2004

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The ferrocene ligand 6‐[(ferrocenylmethyl)amino]‐2‐picoline, FcCH2NHpyMe [Fc = (η5‐C5H5)Fe(η5‐C5H4)], has been prepared by treatment of FcCH2NMe2 with 6‐amino‐2‐picoline, NH2pyMe. The coordination chemistry with group 11 metals has been studied and several complexes with coordination of the metal atom to the pyridine nitrogen atom, such as [M(PPh3)(FcCH2NHpyMe)]OTf, [Au(C6F5)(FcCH2NHpyMe)] and [AuR3(FcCH2NHpyMe)] (M = Au, Ag; R3 = (C6F5)3, (C6F5)2Cl; OTf = trifluoromethanesulfonate), have been obtained. The complex [Cu(FcCH2NHpyMe)2]PF6 has also been synthesised with a probable coordination of the copper centre to the pyridine and amine nitrogen atoms. Deprotonation of the NH group allows the synthesis of dinuclear complexes of the type [M2(PPh3)2(FcCH2NpyMe)]X or [Au2(C6F5)(PPh3)(FcCH2NpyMe)] with a mixed pyridine−amide ligand. Some of the complexes have been characterised by X‐ray diffraction and show the presence of intramolecular aurophilic interactions in the dinuclear complex and intermolecular interactions leading to chains in the mononuclear complex. Other types of secondary bonds are present in these structures, such as hydrogen bonding and weak η2 interactions between the gold centre and the cyclopentadienyl ring. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Synthesis Of the Complexesmentioning

confidence: 99%

“…[1] This can be rationalised in terms of incompatibility between the soft metal centre and the hard nitrogen donor. Additional stabilisation of these compounds may be provided by aurophilic interactions or by formation of NϪH···X hydrogen bonds.…”

Section: Introductionmentioning

confidence: 99%

The Role of Secondary Interactions in Group 11 Metal Complexes Containing the Ferrocene Ligand FcCH₂NHpyMe in Supramolecular Structures

et al. 2004

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“…After 3 days, yellow crystalline blocks were observed. Synthesis of (C^N^C)AuOAu(C^N^C) (5). A solution of 1 (100 mg, 0.18 mmol) in dry acetone (20 ml) was stirred for 16 h at 60°C.…”

Section: Methodsmentioning

confidence: 99%

“…A number of computational studies modelling oxidation reactions envisage the formation and interconversion of species with Au-O-O-Au, Au-OOH and Au-O-Au linkages [16][17][18] . To-date, there is, however, very little precise information available on the structures and bonding of such species; and although a number of gold oxo and hydroxo complexes have been reported 5 0 -bipyridyl and bipy a substituted 2,2 0 -bipyridyl [23][24][25][26][27][28][29][30][31], to the best of our knowledge isolable peroxo, hydroperoxo and alkylperoxo complexes of gold (in any oxidation state) were unknown.…”

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confidence: 99%

“…The mode of oxygen activation remains unclear, not least as Au-O bonds are thought to be intrinsically weak and in general thermally unstable 5 , and the surfaces of gold catalysts adsorb O 2 only to a very limited extent 6 . It has been proposed that negatively charged gold nanoclusters facilitate O 2 adsorption by electron transfer to give surface superoxo-like species [4][5][6][7][8][9][10][11][12] , whereas Gates and co-workers 13 , and Hutchings et al 14 , showed that high-activity gold catalysts for CO oxidation contain species in higher oxidation states (Au þ , Au 3 þ ). A very recent study postulated that Au 3 þ peroxides and oxides are key intermediates in the electrochemical water splitting on gold electrodes 15 .…”

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Gold peroxide complexes and the conversion of hydroperoxides into gold hydrides by successive oxygen-transfer reactions

et al. 2013

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Gold catalysts are widely studied in chemical and electrochemical oxidation processes. Computational modelling has suggested the participation of Au-OO-Au, Au-OOH or Au-OH surface species, attached to gold in various oxidation states. However, no structural information was available as isolable gold peroxo and hydroperoxo compounds were unknown. Here we report the syntheses, structures and reactions of a series of gold(III) peroxides, hydroperoxides and alkylperoxides. The Au-O bond energy in peroxides is weaker than in oxides and hydroxides; however, the Au-OH bond is also weaker than Au-H. Consequently Au-OH compounds are capable of oxygen-transfer generating gold hydrides, a key reaction in a water splitting cycle and an example that gold can react in a way that other metals cannot. For the first time it has become possible to establish a direct connection from peroxides to hydrides: Au-OO-Au-Au-OOH-Au-OH-Au-H, via successive oxygen-transfer events.

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Silver: Inorganic & Coordination ChemistryBased in part on the article Silver: Inorganic & Coordination Chemistry by W. Ewen Smith which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Mak

Zhao

2005

Encyclopedia of Inorganic Chemistry

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The present review is a complete rewrite of the original article in the first edition. The new version provides concise and up‐to‐date information on the inorganic and coordination compounds of silver in oxidation states ranging from subvalent to Ag(IV). Literature coverage is extended to October 2004, and pertinent references are listed for the convenience of the interested reader. The presentation is organized under the following headings: 1. Introduction; 2. Subvalent silver compounds; 3. Silver(I) compounds (under subheadings: 3.1 Halides and pseudohalides; 3.2 Phosphorus donor ligands; 3.3 Nitrogen donor ligands; 3.4 Oxygen donor ligands; 3.5 Chalcogen donor ligands; 3.6 Silver‐rich compounds); 4. Silver(II) compounds; 5. Silver(III) and silver(IV) compounds; 6. Catalysis. The structural features of the compounds are described, and specific examples are illustrated with five figures. For the most important +1 oxidation state of silver, particular emphasis is placed on recent highlights and advances in new areas such as double and multiple salts of silver, silver(I) polyhedra with encapsulated acetylenediide (C 2 2− ) species (symbolized as C 2 @Ag n ), argentophilic Ag(I)⋯Ag(I) interaction in supramolecular assembly, halide‐centered Ag n cages, mixed‐metal clusters, and silver‐rich chalcogenide supercluster complexes. Modern application of inorganic silver catalysts, of both achiral and chiral types, to organic synthesis is presented with selected examples from the recent literature.

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Silver and Gold

Cited by 81 publications

References 3,086 publications

The Role of Secondary Interactions in Group 11 Metal Complexes Containing the Ferrocene Ligand FcCH₂NHpyMe in Supramolecular Structures

The Role of Secondary Interactions in Group 11 Metal Complexes Containing the Ferrocene Ligand FcCH₂NHpyMe in Supramolecular Structures

Gold peroxide complexes and the conversion of hydroperoxides into gold hydrides by successive oxygen-transfer reactions

Silver: Inorganic & Coordination ChemistryBased in part on the article Silver: Inorganic & Coordination Chemistry by W. Ewen Smith which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

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Silver and Gold

Cited by 81 publications

References 3,086 publications

The Role of Secondary Interactions in Group 11 Metal Complexes Containing the Ferrocene Ligand FcCH2NHpyMe in Supramolecular Structures

The Role of Secondary Interactions in Group 11 Metal Complexes Containing the Ferrocene Ligand FcCH2NHpyMe in Supramolecular Structures

Gold peroxide complexes and the conversion of hydroperoxides into gold hydrides by successive oxygen-transfer reactions

Silver: Inorganic & Coordination ChemistryBased in part on the article Silver: Inorganic & Coordination Chemistry by W. Ewen Smith which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

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The Role of Secondary Interactions in Group 11 Metal Complexes Containing the Ferrocene Ligand FcCH₂NHpyMe in Supramolecular Structures

The Role of Secondary Interactions in Group 11 Metal Complexes Containing the Ferrocene Ligand FcCH₂NHpyMe in Supramolecular Structures