Observation of a P/M interconversion of a goldâ€“phosphine helicate via â€‰ 31P NMR

Schuh, Walter; Kopacka, Holger; Wurst, Klaus; Péringer, Paul

doi:10.1039/b106058a

Cited by 25 publications

(35 citation statements)

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“…Variable temperature 31 P NMR experiments have been carried out in order to estimate the strength of this interaction based on the calculated height of the barrier of interconversion between the syn and anti forms of the compound [240]. Nido-carboranes may act as bridging Bidentate diphosphines, such as bis(diphenylphosphino)methane (dppm) [242][243][244], 1,2-bis(diphenylphosphino)ethane (dppe) [245], 1,2-bis(hydroxymethylphosphino)ethane (hmpe) [246], 1,2-bis(dicyclohexyphosphine)ethane (dcype) [247] or bis(diphenylphosphino)isopropane (dppip) [248] build structures of stoichiometry [Au 2 (P$P) 2 ] 2þ such as those shown in Figure 2.45. The crystal structure of [Au 2 (dmpe) 2 ]X 2 ÁnH 2 O (dmpe ¼ 1,2-bis(dimethylphosphino)ethane; X ¼ Cl, n ¼ 2; Br, n ¼ 1.5) consist of polymeric chains anion/water molecule/cation/anion/cation/anion/water molecule [249].…”

Section: Complexes With Bridging Bidentate Ligandsmentioning

confidence: 99%

“…In addition, heterometallic complexes containing gold and iridium or gold and ruthenium with similar patterns, but with two different metal centers, have been described and their luminescent properties also studied. The fluxional behavior in solution of compound [Au 2 (TP) 2 ] 2þ has been studied by NMR [245,[342][343][344][345][346][347][348][349][350][351][352][353][354].…”

Section: Complexes With Bridging Bidentate Ligandsmentioning

confidence: 99%

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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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Section: Complexes With Bridging Bidentate Ligandsmentioning

confidence: 99%

Section: Complexes With Bridging Bidentate Ligandsmentioning

confidence: 99%

Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

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“…The helical twist in the trinuclear helicate [Au 3 (µ 3 -pp2) 2 ](OTf) 3 (pp2 ϭ PhP(CH 2 CH 2 PPh 2 ) 2 ] is between 50.66(7)°and 54.57(6)°. [8] The helicates are unsaturated in view of the gold-gold distances, which all are within the range of AuϪAu d 10 -d 10 interactions. [9] The separation of the inner Au centers (3.33 Å , mean value) is significantly larger than the contact between inner and outer gold atoms (3.09 Å , mean value).…”

Section: Resultsmentioning

confidence: 99%

“…The remaining two OTf anions are between the sheets without any contacts to gold atoms. Steric reasons may control the formation of helicates or meso-helicates: A geometrical extrapolation of [Au 3 (µ 3 -pp2) 2 ](OTf) 3 [8] does not exclude the formation of a helical structure from (R,S)-p4 ligands. In fact, a meso-helicate is observed for 1.…”

Section: Resultsmentioning

confidence: 99%

“…Related effects are present in [Au 3 (µ 3 -pp2) 2 ](OTf) 3 . [8] More data is available on the control of the formation of triple-stranded helicates or meso-helicates from achiral ligands. This is related to the rigidity and the form (S or C type) of the ligands, the nature of the spacer (even or odd number of alkylene chains and the chirality of the spacers) and the presence of suitable templates.…”

Section: Resultsmentioning

confidence: 99%

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Homochiral Self Recognition in Gold-Phosphane-Helicates

Schuh

Kopacka

Wurst

et al. 2002

Eur. J. Inorg. Chem.

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Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

Engesser

Friedmann

Martens

et al. 2016

Chemistry A European J

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A series of gold acetonitrile complexes [Au(NCMe) ] [WCA] with weakly coordinating counterions (WCAs) was synthesized by the reaction of elemental gold and nitrosyl salts [NO] [WCA] in acetonitrile ([WCA] =[GaCl ] , [B(CF ) ] , [Al(OR ) ] ; R =C(CF ) ). In the crystal structures, the [Au(NCMe) ] units appeared as monomers, dimers, or chains. A clear correlation between the aurophilicity and the coordinating ability of counterions was observed, with more strongly coordinating WCAs leading to stronger aurophilic contacts (distances, C-N stretching frequencies of [Au(NCMe) ] units). An attempt to prepare [Au(L) ] units, even with less weakly basic solvents like CH Cl , led to decomposition of the [Al(OR ) ] anion and formation of [NO(CH Cl ) ] [F(Al(OR ) ) ] . All nitrosyl reagents [NO] [WCA] were generated according to an optimized procedure and were thoroughly characterized by Raman and NMR spectroscopy. Moreover, the to date unknown species [NO] [B(CF ) CN] was prepared. Its reaction with gold unexpectedly produced [Au(NCMe) ] [Au(NCB(CF ) ) ] , in which the cyanoborate counterion acts as an anionic ligand itself. Interestingly, the auroborate anion [Au(NCB(CF ) ) ] behaves as a weakly coordinating counterion, which becomes evident from the crystallographic data and the vibrational spectral characteristics of the [Au(NCMe) ] cation in this complex. Ligand exchange in the only room temperature stable salt of this series, [Au(NCMe) ] [Al(OR ) ] , is facile and, for example, [Au(PPh )(NCMe)] [Al(OR ) ] can be selectively generated. This reactivity opens the possibility to generate various [AuL L ] [Al(OR ) ] salts through consecutive ligand-exchange reactions that offer access to a huge variety of Au complexes for gold catalysis.

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Observation of a P/M interconversion of a goldâ€“phosphine helicate via â€‰ 31P NMR

Abstract: Ligands containing P-CH2-CH2-P elements have been shown to form double-stranded helicates whose axis consists of gold atoms with Au...Au contacts; the interconversion of the P and M forms of the helicate [Au3(mu-pp2)2](OTf)3 (pp2 = PhP(CH2CH2PPh2)2) is monitored via 31P NMR.

Cited by 25 publications

References 5 publications

Gold–Gold Interactions

Gold–Gold Interactions

Homochiral Self Recognition in Gold-Phosphane-Helicates

Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

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