Gold(I) dimethyl- and diphenyl-dithiophosphinate complexes

Preisenberger, Max; Bauer, Andreas; Schier, Annette; Schmidbaur, Hubert

doi:10.1039/a706033e

Cited by 29 publications

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“…D uring a study o f raw//muclear gold com plexes o f thiophosphonates, thiophosphinites and related com pounds we have now encountered another group of com pounds, where m inor variations in the com position have a m arked influence on the supram olecular structure. These results are pre sented here as a supplem ent to our previous per tinent com m unications [21,22]. W ith tw o equivalents of the oxonium salt the 2:1 com plexes w ere obtained in high yields (85-95% ), and w ith three equivalents the corresponding trin uclear com pounds were generated (60-75% yield) (Schem e 1).…”

Section: Introductionmentioning

confidence: 90%

“…W ith tw o equivalents of the oxonium salt the 2:1 com plexes w ere obtained in high yields (85-95% ), and w ith three equivalents the corresponding trin uclear com pounds were generated (60-75% yield) (Schem e 1). Sim ilar results were obtained previ ously with diorganophosphinic and organophosphonic acids [22], The products were isolated by crystallization as colourless, air-stable solids, soluble in di-and trichlorom ethane. Their com position was confirm ed by elem ental analysis and by FAB m ass spectro-0932-0776/98/0800-0781 $ 06.00 © 1998 Verlag der Zeitschrift für Naturforschung.…”

Section: Introductionmentioning

confidence: 97%

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Variations in the Chain Structure of Cationic (Phosphine)gold(I) Dialkyldithiophosphate Complexes

Preisenberger

Schier

Schmidbaur

1998

Zeitschrift Für Naturforschung B

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Treatment of dithiophosphoric acid diesters (RO)2P(S)SH with appropriate quantities of tris[(phosphine)gold(I)]oxoniumtetrafluoroborates {[(R'3P)Au]30}+ BF4_ in dichloromethane gives di-or trinuclear complexes of the types {(RO)2P[SAu(PR'3)]2/ 3}+/2+ (2) BF4~ as colour less, crystalline salts. As determined by single crystal X-ray diffraction studies, in the 1:2 complexes (with R = R' = Me and R' = Et, R = Ph and o-Tol), each gold atom is attached to a different sulfur atom, but with short intracationic Au-Au contacts. These cations are associated to form strings through intermolecular Au-Au contacts in the first case (R = Et), but through additional Au-S contacts in the second (R = Ph). For R = o-Tol, the cations are not associated at all owing to steric hindrance. This result is indicative of very small energy differences between the two modes of association. The 1:3 complexes are fluxional in solution and show virtually equivalent R3PAU groups in the NMR spectra at 20°C, but at low temperature non-equivalent ligands can be distinguished as shown previously for analogous dithiophosphinate derivatives.

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Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 97%

Variations in the Chain Structure of Cationic (Phosphine)gold(I) Dialkyldithiophosphate Complexes

Preisenberger

Schier

Schmidbaur

1998

Zeitschrift Für Naturforschung B

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“…Aurophilic interactions lead to dimers in [Au(OCOMe)(PR 3 )] (PR 3 tris(2-thienyl)phosphine) and are absent in the chloride complexes [AuCl(ER 3 )] (ER 3 ¼ tris(2-thienyl)phosphine, tris(2-thienyl)arsine, tri-(2-fuyl)phosphine) [25]. Other anionic ligands in complexes [AuX(PPh 3 )] which crystallize as dimers include chalcogenolates [21,[26][27][28][29], an example is shown in Figure 2.4, or diphenyldithiophosphinate ligands [30]. Some phosphine thiolate complexes of stoichiometry [Au (SR)L] (SR ¼ phenylthiolate; phenylthiolate OMe or Cl substituted; L ¼ PPh 3 , TPA) have been studied with the aim of rationalizing the relation between the gold-gold distance and the energies of the luminescent emissions [31].…”

Section: Dinuclear Aggregatesmentioning

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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“…Recent quantum-chemical calculations including relativistic and correlation effects have indicated that the bond energy is a function of the nature of the sub stituents at the gold atoms, and that thiolate and iodide ligands are predicted to yield optimum bond strength [12 ]. This conclusion has not been fully supported by subsequent experimental investigations, where Au -S interactions were found to be competing favourably with Au -Au interactions [13]. The evaluation of a specific structure is generally not straightforward since weak forces such as those arising from aurophilicity are easily overruled by steric crowding in the aggregates and by compli cated packing features of the individual crystal.…”

Section: Introductionmentioning

confidence: 74%

The Structural Chemistry of GoId(I) Quinoline-2-thiolate and Iodide Complexes of Polytertiary Phosphines

Tzeng

Zank

Schier

et al. 1999

Zeitschrift Für Naturforschung B

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Treatment of (chloro)gold(I) complexes of di-and tetra-tertiary phosphines with equivalent quantities of sodium quinoline-2-thiolate in methanol / dichloromethane affords the correspond ing (phosphine)gold(I) quinoline-2-thiolates in high yields. The di-and tetranuclear complexes, respectively, of a,u>bis(diphenylphosphino)-propane (1), -butane (2) and -pentane (3) and of tris(2-diphenylphosphino-ethyl)phosphine (4) have been obtained as crystalline solids, and the structures of 2 and 4 have been determined by single crystal X-ray diffraction studies. Un expectedly, the molecules of 2 are loosely aggregated into strings via weak intermolecular gold-sulfur, not via Au-Au interactions. Compound 4 is a monomeric tetranuclear cluster in the solid state with two intramolecular gold-gold bonds. Bis(2-diphenylphosphino-ethyl)-phenylphosphine (PPP) forms trinuclear complexes with gold(I) chloride, bromide and iodide (5a -c). The iodide complex features a chain structure through intermolecular Au -Au contacts between the two terminal P-Au-I units. The closest contacts between the chains are determined by Au-I and I -I interactions of the central P-Au-I unit.

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Gold(I) dimethyl- and diphenyl-dithiophosphinate complexes

Cited by 29 publications

References 29 publications

Variations in the Chain Structure of Cationic (Phosphine)gold(I) Dialkyldithiophosphate Complexes

Variations in the Chain Structure of Cationic (Phosphine)gold(I) Dialkyldithiophosphate Complexes

Gold–Gold Interactions

The Structural Chemistry of GoId(I) Quinoline-2-thiolate and Iodide Complexes of Polytertiary Phosphines

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