Stabilisation of AuIII and AuI in the same complex molecule by a tridentate phosphinodithiolate ligand. Structures of [AuIIILCl] and [AuIL2AuIII] (L = {PhP(C6H3S-2-SiMe3-3)2}2−)

Ortner, Kirstin; L, Hilditch; Dilworth, Jonathan R.; Abram, Ulrich

doi:10.1016/s1387-7003(98)00126-9

Cited by 10 publications

(3 citation statements)

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“…Reduction of the gold is obviously inhibited, and the compounds [AuCl( L 1 )] are formed in reasonable yields. Partial reduction of gold and the formation of the mixed-valent complex 3 is only observed as a side reaction . [AuCl{PhP(C 6 H 3 −S-2−SiMe 3 -3) 2 }] ( 2 ) could be isolated in crystalline form, whereas with {PhP(C 6 H 4 −S-2) 2 } only a red oil was obtained and all our attempts to crystallize this compound failed.…”

Section: Resultsmentioning

confidence: 99%

“…A compound of the composition [Au 2 L 1b 2 ] ( 4 ) has been isolated in crystalline form. Its structure (Figure ) corresponds to that of the mixed-valence side-product of the reaction of [Au(damp-C 1 ,N)Cl 2 ] with L 1a . Selected bond lengths and angles of the binuclear complex are given in Table .…”

Section: Resultsmentioning

confidence: 99%

“…Crystal data and more details of the data collections and refinements are contained in Table . Additional information on the structure determinations of compounds 2 and 3 is contained in ref and has been deposited with the Fachinformationszentrum Karlsruhe as CSD 410274 ( 2 ) and CSD 410275 ( 3 ).…”

Section: Methodsmentioning

confidence: 99%

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Gold Complexes with Potentially Tri- and Tetradentate Phosphinothiolate Ligands

Ortner

Zheng

et al. 2000

Inorg. Chem.

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Reactions of [Au(PPh3)Cl], (Bu4N)[AuCl4] and the organometallic gold complex [Au(damp-C1,N)Cl2] (damp- = 2-(N,N-dimethylaminomethyl)phenyl) with the potentially tri- and tetradentate proligands PhP(C6H3-SH-2-R-3)2 (H2L1a, R = SiMe3; H2L1b, R = H) and P(C6H4-SH-2)3 (H3L2) result in the formation of mono- or dinuclear gold complexes depending on the precursor used. Monomeric complexes of the type [AuL1Cl] are formed upon the reaction with [Au(damp-C1,N)Cl2], but small amounts of dinuclear [AuL1]2 complexes with gold in two different oxidation states, +1 and +3, have been isolated as side-products. The dinuclear compounds are obtained in better yields from [AuCl4]-. A dinuclear complex having two Au(III) centers can be isolated from the reaction of [Au(PPh3)Cl] with H3L2, whereas from the reaction with H2L1b the mononuclear [Au(Ph3P)HL1b] is obtained, which contains a three-coordinate gold atom. Comparatively short gold-gold distances have been found in the dinuclear complexes (2.978(2) and 3.434(1) A). They are indicative of weak gold-gold interactions, which is unusual for gold(III).

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Gold Complexes with Potentially Tri- and Tetradentate Phosphinothiolate Ligands

Ortner

Zheng

et al. 2000

Inorg. Chem.

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PPh(2-C6H4S)2 as a Pincer Ligand in Nickel(II) and Palladium(II) Complexes — X-ray Structure of [Ni{PPh(C6H4S)2}(PPh2Me)], [Pd2(μ-dppe){PPh(C6H4S)2}2] and [Ni{PPh(C6H4S)2}]2

Cerrada

Falvello

Hursthouse

et al. 2002

Eur. J. Inorg. Chem.

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The phosphanylthiol PPh(2-C 6 H 4 SH) 2 reacts with the Ni II and Pd II complexes [MCl 2 L 2 ] in the presence of NaOEt to give the mononuclear derivatives [M{PPh(C 6 H 4 S) 2 }L] [M = Ni, L = PPh 3 (1), PPh 2 Me (2); M = Pd, L = PPh 3 (3)]. The analogous reaction starting with complexes containing bidentate ligands [MX 2 (L-L)] produces different results depending on the ligand used. The complexes [M{PPh(C 6 H 4 S) 2 }(dppm)] [M = Ni (4), Pd (5)], with an unligated phosphorus atom in the diphosphane are obtained with bis(diphenylphosphanyl)methane (dppm), while the dinuclear complexes [M 2 (µ-dppe){PPh(C 6 H 4 S) 2 }] [M = Ni (6), Pd

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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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Stabilisation of AuIII and AuI in the same complex molecule by a tridentate phosphinodithiolate ligand. Structures of [AuIIILCl] and [AuIL2AuIII] (L = {PhP(C6H3S-2-SiMe3-3)2}2−)

Cited by 10 publications

References 21 publications

Gold Complexes with Potentially Tri- and Tetradentate Phosphinothiolate Ligands

Gold Complexes with Potentially Tri- and Tetradentate Phosphinothiolate Ligands

PPh(2-C6H4S)2 as a Pincer Ligand in Nickel(II) and Palladium(II) Complexes — X-ray Structure of [Ni{PPh(C6H4S)2}(PPh2Me)], [Pd2(μ-dppe){PPh(C6H4S)2}2] and [Ni{PPh(C6H4S)2}]2

Gold–Gold Interactions

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