Strong Closed-Shell Interactions in Inorganic Chemistry.

The structure of thallium dicyanoargentate(I) has been determined crystallographically. The crystal structure shows an Ag−Ag distance of 3.11 A. This is the shortest Ag−Ag distance reported for any silver dicyanide salt whose crystal structure has been determined. Raman spectra of the compound show four νC-N peaks that are well-resolved in the 10−80 K temperature range. This result agrees well with group theory analysis. Extended Huckel calculations using relativistic wave functions have been carried out for two models which describe the interactions between the Ag(CN)2- ions within the crystal structure of Tl[Ag(CN)2]. The results of these calculations indicate the formation of potential wells at short Ag−Ag distances. The data in this study suggest the significance of ligand-unsupported silver−silver interactions (argentophilicity) in Tl[Ag(CN)2]. Tl−Ag interactions are determined to be insignificant in the compound. Tl[Ag(CN)2] crystallizes in the monoclinic space group P21/c (No. 14), with a = 7.798(1...

Crystal Structure, Electronic Structure, and Temperature-Dependent Raman Spectra of Tl[Ag(CN)2]: Evidence for Ligand-Unsupported Argentophilic Interactions

Three- and Four-Coordinate Gold(I) Complexes.

The coordination chemistry of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) and isologs

Reductive elimination of carbon-carbon bonds occurs in numerous metal-catalysed reactions. This process is well documented for a variety of transition metal complexes. However, carbon-carbon bond reductive elimination from a limited number of Au(III) complexes has been shown to be a slow and prohibitive process that generally requires elevated temperatures. Herein we show that oxidation of a series of mono- and bimetallic Au(I) aryl complexes at low temperature generates observable Au(III) and Au(II) intermediates. We also show that aryl-aryl bond reductive elimination from these oxidized species is not only among the fastest observed for any transition metal, but is also mechanistically distinct from previously studied alkyl-alkyl and aryl-alkyl reductive eliminations from Au(III).

/pdf/exceptionally-fast-carbon-carbon-bond-reductive-elimination-3ri21x9ycp.pdf

Exceptionally fast carbon–carbon bond reductive elimination from gold( III )

Trinuclear Au2Ag and Au2Cu Complexes with Mesityl Bridging Ligands. X-ray Structure of the Chain Polymer [{Au(μ-mes)AsPh3}2Ag](ClO4)

The reactions of Na2dmit (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate) with AuClL in 1:2 ratios lead to [Au2(dmit)L2] [L = PPh3 (1), PPh2Me (2), PPhMe2 (3), PMe3 (4), CH2PPh3 (5), CH2PPh2Me (6), CH2PPhMe2 (7)]. Complexes 1, 2, and 5 react further with equimolecular amounts of [AuL(tht)]ClO4 (tht = tetrahydrothiophene), affording trinuclear complexes [Au3(dmit)L3]ClO4 (8−10). When the reactions of Na2dmit with AuClL are carried out in 1:1 ratios and in the presence of NBu4Br, mononuclear tricoordinated gold(I) complexes NBu4[Au(dmit)L] [L = PPh3 (11), PPh2Me (12), PMe3 (13)] are obtained. Other anionic derivatives such as (PPN)2[Au2(dmit)X2] [X = C6F5 (14), Cl (15a), Br (15b)] can be obtained either by reaction of Na2dmit with Q[Au(C6F5)X] in 1:2 ratio or by addition of (PPN)X to the recently reported [Au2(dmit)(AsPh3)]. Oxidative reactions of 11, 12, and 14 or 15b with excess (TTF)3(BF4)2 afford (TTF)2[Au(dmit)2] (16), (TTF)[Au2(dmit)(C6F5)2] (17), and (TTF)3[Au2(dmit)Br2] (18), respectively. Reaction of ...

Synthesis and Reactivity of Heteroleptic Complexes of Gold with 2-Thioxo-1,3-dithiole-4,5-dithiolate (dmit). X-ray Structure of [Au2(μ-dmit)(PPh3)2], (NBu4)[Au(dmit)(PPh3)], and (PPN)[Au(dmit)(C6F5)2]

Polynuclear mesityl-gold and -gold-silver derivatives. Crystal structure of [Ag(μ-dppm)2{Au(mes)}2]C1O4 · 3CH2Cl2 (dppm = bis(diphenylphosphino)methane, mes=mesityl)

A. Laguna

Papers

Trinuclear Au2Ag and Au2Cu Complexes with Mesityl Bridging Ligands. X-ray Structure of the Chain Polymer [{Au(μ-mes)AsPh3}2Ag](ClO4)

Synthesis and Reactivity of Heteroleptic Complexes of Gold with 2-Thioxo-1,3-dithiole-4,5-dithiolate (dmit). X-ray Structure of [Au2(μ-dmit)(PPh3)2], (NBu4)[Au(dmit)(PPh3)], and (PPN)[Au(dmit)(C6F5)2]

Polynuclear mesityl-gold and -gold-silver derivatives. Crystal structure of [Ag(μ-dppm)2{Au(mes)}2]C1O4 · 3CH2Cl2 (dppm = bis(diphenylphosphino)methane, mes=mesityl)

Unexpected ring-opening reaction to a new cyanamide-thiolate ligand stabilized as a dinuclear gold complex

Trimethylsilylmethyl gold(I) complexes. X-ray structure of [Au(CH2SiMe3)PPh2CH2PPh2Me]ClO4 · 0.25CH2Cl2