Synthesis and structural characterization of the gold complex, [n-Bu4N]2[Au2(i-MNT)2] (i-MNT = 1,1-dicyanoethylene-2,2-dithiolate) and its oxidative-addition products [Ph4As]2[Au2(i-MNT)2Cl2], [n-Bu4N]2[Au2(i-MNT)2Br2], and [n-Bu4N][Au(i-MNT)2]. Spectral studies of the disproportionation of [n-Bu4N]2[Au2(i-MNT)2X2] (X = Cl-, Br-, I-) into [n-Bu4N][AuX2] and [n-Bu4N][Au(i-MNT)2]

Khan, M. Nazrul I.; Wang, Suning; Fackler, John P.

doi:10.1021/ic00317a036

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“…90 %) component, assigned as 2 D , but no hydride resonance. The X-ray crystal structure [13] confirms that 2 is monomeric in the solid state ( Figure 1), with the shortest gold-gold separations in the crystal measured at 8.9174 (7) . A minor byproduct (ca.…”

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confidence: 56%

“…[12] In the IR spectrum of 2 D , no band is observed at 1976 cm À1 , and the expected AuÀD stretch at 1407 cm À1 appears to be obscured by bands resulting from ligand-derived stretching modes. The X-ray crystal structure [13] confirms that 2 is monomeric in the solid state ( Figure 1), with the shortest gold-gold separations in the crystal measured at 8.9174 (7) . When Solid-state structure of 2·(C 5 H 12 ); thermal ellipsoids are set at the 50 % probability level.…”

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confidence: 56%

“…A single-crystal X-ray diffraction study of 6, prepared in this manner, confirmed its structure as an a-metalated diazo compound (Figure 4). [13] The distance between the Au center and the diazoalkyl carbon atom (2.0328(19) ) is similar to the AuÀC NHC distance of 2.0069 (16) ; the diazoalkyl group displays a short N À N bond (1.134 (3) ) and a rather long N À C bond (1.311 (3) ).…”

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confidence: 77%

“…Analysis of the complex by X-ray crystallography ( Figure 2) [13] revealed that 4, the isolobal analogue of H 3 + , has a triangular structure [7] with a notably short intramolecular Au I ÀAu I separation (2.7099 (4) ) compared to typical AuÀAu distances in aurophilic interactions or in metallic gold. [14] Complex 4 is stable to air and water in the solid state.…”

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confidence: 99%

“…[15] Although 2 displayed no reactivity toward alkynes such as 3-hexyne and diphenylacetylene at room temperature, it reacted cleanly with 1.05 equivalents dimethyl acetylenedicarboxylate (DMAD) in benzene to form the vinylgold complex 5. The crystal structure of 5 ( Figure 3) [13] reveals a trans orientation of the gold and hydrogen atoms about the double bond. The trans insertion of alkynes into various transition metal hydride complexes has been proposed to occur through a variety of mechanisms.…”

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Reactions of a Stable Monomeric Gold(I) Hydride Complex

2008

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Reactions of a Stable Monomeric Gold(I) Hydride Complex

2008

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Rearrangement of Gold and Silver Complexes

Wang

Fackler

2009

Patai's Chemistry of Functional Groups

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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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Reactions of a Stable Monomeric Gold(I) Hydride Complex

Reactions of a Stable Monomeric Gold(I) Hydride Complex

Rearrangement of Gold and Silver Complexes

Gold–Gold Interactions

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