Synthesis, structure, and electronic spectroscopy of neutral, dinuclear gold(I) complexes. Gold(I)-gold(I) interactions in solution and in the solid state

Narayanaswamy, Ratnavathany; Young, Michelle; Parkhurst, Erica; Ouellette, M.; Kerr, Margaret E.; Ho, Douglas M.; Elder, R. C.; Bruce, Alice E.; Bruce, Mitchell R. M.

doi:10.1021/ic00063a051

Cited by 201 publications

(99 citation statements)

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“…Except when n = 2, this signal moves downfield as the number of connecting carbons (n) in the phosphine ligand backbone increases. Such a trend, also observed previously [25], has been ascribed to small variations in the dihedral or bond angles at the phosphorus atom with increasing alkyl chain length [28,29].…”

Section: Nmr Spectroscopysupporting

confidence: 78%

Amides of gold(I) diphosphines prepared from N-heterocyclic sources and their in vitro and in vivo screening for anticancer activity

Horvath

Dobrzańska

Strasser

et al. 2012

Journal of Inorganic Biochemistry

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Synopsis __________________________________________________________________________Among a new series of gold(I) complexes that contain diphosphine and deprotonated N-heterocyclic ring systems as ligands, the compounds containing diphenyl(phosphino)pentane and pyrazolate (lypophilic) or 1,2,4,-triazolate (hydrophilic) have high anti-tumour specificities. They induce an apoptic cell death pathway and have the maximum tolerated dose of 1.5 μmol/kg when administered to Balb/C mice. ___________________________________________________________________ *Synopsis for the Graphical abstract  In 25 new complexes diphosphines and azolate-type ligands coordinate to gold  Solvent molecules and counterions appear within channels of a crystalline complex  Cytotoxicity is dependent upon aliphatic C chain length in the ligands  An apoptosis cell death with certain mitochondrial involvement is indicated  Tolerated doses compared to [Au(dppe) 2 ]Cl, tumour specificity is much better *Highlights A B S T R A C T ------------------------------------------------------------------------A series of new neutral mononuclear or dinuclear gold(I) complexes and a cyclic cationic tetranuclear amidogold(I) complex comprising of the phosphines 1,2-bis(dimethylphosphino)ethane (dmpe), μ-1,2-bis(diphenylphosphino)ethane (dppe), μ-1,3-bis(diphenylphosphino)propane (dppp), μ-1,5-bis(diphenylphosphino)pentane (dpppe), μ-1,6-bis(diphenylphosphino)hexane (dpph) or trimethylphosphine, and several N-heterocyclic ring systems (imidazolate, pyrazolate, 1,2,3-triazolate, 1,2,4-triazolate, pyrrolate, 9H-purine-9-ate or 9H-purine-6-amine-9-ate) as ligands, reveal intermolecular aurophilic interactions and 2D channels available for solvent molecules in some of their crystal structures. The antitumou r 2 activity of the acyclic gold(I) compounds is highly dependent on the substituents on the phosphorus atoms being highest for phenyl groups and lower for methyl groups. The activity of these compounds against selected cell lines is linked to the length of the carbon bridge between the two phosphorus atoms being highest with a bridge consisting of 5 or 6 carbons. Two compounds with the highest tumour specifities that contain dpppe and pyrazolate (a lipophilic compound) or 1,2,4-triazolate (a hydrophilic compound) induce the apoptic cell death pathway and tolerate a maximum dose of 1.5 μmol/kg when administered to Balb/C mice.

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Section: Nmr Spectroscopysupporting

confidence: 78%

Amides of gold(I) diphosphines prepared from N-heterocyclic sources and their in vitro and in vivo screening for anticancer activity

Horvath

Dobrzańska

Strasser

et al. 2012

Journal of Inorganic Biochemistry

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“…Other examples of complexes [Au 2 X 2 (P$P)] that show similar structures to those in Figure 2.38a include anionic X ligands such as thiolates [211][212][213] or triphenylsilyl [214], with P$P ¼ dppm; X ¼ RC:C (R ¼ Ph, 4-OMe-C 6 H 4 ) with P$P ¼ N,N-bis (diphenylphosphino)propylamine [215]; X ¼ SC(OMe) ¼ NC 6 H 4 -4-(NO 2 ) with P$P ¼ (PPh 2 ) 2 (CH 2 ) n (n ¼ 1-4, no aurophilic interactions are found for n ¼ 4) or dppf [216]; X ¼ [S 2 P(R)(OR)] (R ¼ p-C 6 H 4 -OCH 3 ; R ¼ c-C 5 H 9 ), with P$P ¼ (PPh 2 ) 2 (CH 2 ) n [n ¼ 1-4; only for n ¼ 1 intramolecular interactions are present, for the other three Other derivatives with thiolates as anionic ligands which display chain structures are [Au 2 (SR) 2 (P$P)] (R ¼ Ph, P$P ¼ 1,2-bis(diphenylphosphino)ethene; R ¼ S-p-4-Me-C 6 H 4 , P$P ¼ PPh 2 (CH 2 ) 5 PPh 2 ) and [Au 2 Cl(SPh)(P$P)] (P$P ¼ 1,2-bis(diphenylphosphino)ethene) [26,[218][219][220]. In complexes [Au 2 {SC 6 H 4 -2-(C(¼O) Y)} 2 (m-dppf)], when Y ¼ NHMe intermolecular interactions lead to the formation of chains (Figure 2.40c).…”

Section: Complexes With Bridging Bidentate Ligandsmentioning

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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“…Besides, dynamic systems were successfully investigated by solution NMR. 7 Recently, we reported that the [Au 2 xantphos 2 ] NO 3 2 gold(I) complex (1) derived from the 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (xantphos) ligand exhibits Ł Correspondence to: Gábor Tárkányi, Institute of Structural Chemistry, Chemical Research Center of the Hungarian Academy of Sciences, Pusztaszeriút 59-67, H-1025 Budapest, Hungary. E-mail: gtarkanyi@chemres.hu such an AuÐ Ð ÐAu aurophilic interaction in the solid state.…”

Section: Introductionmentioning

confidence: 99%

Conformational analysis of a helically distorted gold(I) macrocycle derived from xantphos: evidence for the aurophilic Au… Au interaction from NMR

Tárkányi

Király

Pálinkás

et al. 2007

Magnetic Reson in Chemistry

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Variable-temperature solution (1)H- and (31)P-NMR experiments are reported for [Au(2)(xantphos)(2)](NO(3))(2) gold(I) complex incorporating a 16-membered Au(2)P(4)C(8)O(2) macrocycle derived from the 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (xantphos) ligand. These NMR studies provide detailed structural information about its solution structure in comparison to the solid-state structure available from single crystal X-ray diffraction. Two-dimensional (1)H-NOESY spectroscopy at low temperatures allowed the full assignment of proton resonances, which are severely exchange-broadened at room temperature. The (1)H--(1)H spatial connectivities of the large number of non-equivalent protons unravel the complete stereochemistry of the gold(I) macrocycle in its symmetrically twisted conformation. Chemical exchange between particular proton pairs has allowed understanding the molecular dynamics and ruled out formation of coordination oligomers. Spectral analysis of the unique phosphorous AA'BB' spin system has revealed three-bond (31)P--(31)P scalar couplings mediated through the Au--Au bond, and has confirmed the existence of the aurophilic contact in low-temperature solutions. The solution (13)C and (31)P spectra are compared to the solid state (31)P-MAS and (13)C--CP/MAS spectra, where signal doubling effects due to the crystal packing have been discovered.

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Synthesis, structure, and electronic spectroscopy of neutral, dinuclear gold(I) complexes. Gold(I)-gold(I) interactions in solution and in the solid state

Cited by 201 publications

References 1 publication

Amides of gold(I) diphosphines prepared from N-heterocyclic sources and their in vitro and in vivo screening for anticancer activity

Amides of gold(I) diphosphines prepared from N-heterocyclic sources and their in vitro and in vivo screening for anticancer activity

Gold–Gold Interactions

Conformational analysis of a helically distorted gold(I) macrocycle derived from xantphos: evidence for the aurophilic Au… Au interaction from NMR

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