Synthesis of [Au(NH3)2]+ salts and the crystal structure of [Au(NH3)2]Br

Mingos, D. Michael P.; Yau, J.K.F.; Menzer, Stephan; Williams, David J.

doi:10.1039/dt9950000319

Cited by 52 publications

(40 citation statements)

References 2 publications

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“…[32,34] In apreviously reported procedure, 1d was synthesized through metathesis of Li + [Al(OR F ) 4 [19] chain:t riple [20] and quadruple units; [21] octahedron:[P(AuPPh 3 ) 6 ] 3 + ; [22] [Au 2 (dppe) 2 ] 2 + ([OTf] À ) 2 ; [27] [Au 2 (SMe 2 ) 4 ] 2 + [SbF 6 ] 2 (contains two independent dimers:3.139(2) and 3.087(2) ;a verage 3.113 ); [19] [Au 2 (NH 3 ) 4 ]Br 2 . [28] gaseous NO andN O 2 in liquid SO 2 giving 1d in 85 %y ield. [35] We investigated the metathesiso fL i + [Al(OR F ) 4 ] À with the commerciallya vailable, reasonablyp riced nitrosyl salt [NO] + [BF 4 ] À (1a)-an approach used in recent years for the synthesis of [NO] + salts of WCAs like [HCB 11 Cl 11 ] À [36] and [B 12 Cl 12 ] 2À [37] and [Me 3 NB 12 Cl 12 ] À [Eq.…”

Section: Synthesis Of Nitrosyl Salts Of Weakly Coordinating Anionsmentioning

confidence: 99%

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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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Section: Synthesis Of Nitrosyl Salts Of Weakly Coordinating Anionsmentioning

confidence: 99%

“… Dimeric structures of [Au(L) 2 ] + cations (distances in Å). Examples: [Au 2 (dppe) 2 ] 2+ ([OTf] − ) 2 ; [Au 2 (SMe 2 ) 4 ] 2+ [SbF 6 ] 2 (contains two independent dimers: 3.139(2) and 3.087(2) Å; average 3.113 Å); [Au 2 (NH 3 ) 4 ]Br 2 …”

Section: Introductionmentioning

confidence: 99%

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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“…Apart from structure and bonding aspects, another impetus to pursue chemistry of heterocyclic‐2‐thiones lies in their biochemical applications 1–6. Metal complexes are known to have applications, as antimetabolite and antitumor drugs, they also exhibit bacteriocidal and fungicidal activity 22–24. Aurophosphine thiolate complexes have shown antiarthritic activity, and they are also used as anticancer drugs 25–28…”

Section: Introductionmentioning

confidence: 99%

1, 9‐Dihydro‐purine‐6‐thione Derivatives of the d⁸–d¹⁰ Metal Ions (Pd^II, Pt^II, and Cu^I): Synthesis, Spectroscopy, and Structures

Lobana

Kaur

Hundal

et al. 2012

Zeitschrift anorg allge chemie

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Reaction of 1,9-dihydro-purine-6-thione (puSH 2 ) in presence of aqueous sodium hydroxide with PdCl 2 (PPh 3 ) 2 suspended in ethanol formed [Pd(κ 2 -N 7 ,S-puS)(PPh 3 ) 2 ] (1). Similarly, complexes [Pd(κ 2 -N 7 ,S-puS)(κ 2 -P,P-L-L)] (2-4) {L-L = dppm (m = 1) (2), dppp (m = 3) (3), dppb (m = 4) (4)} were prepared using precursors the [PdCl 2 (L-L)] {L-L = Ph 2 P-(CH 2 ) m -PPh 2 }. Reaction of puSH 2 suspended in benzene with platinic acid, H 2 PtCl 6 , in ethanol in the presence of triethylamine followed by the addition of PPh 3 yielded the complex [Pt(κ 2 -N 7 ,S-puS)(PPh 3 ) 2 ] (5). Complexes [Pt(κ 2 -N 7 ,S-puS)-(κ 2 -P,P-L-L)] (6-8) {L-L = dppm (6), dppp (7), dppb (8)} were pre-* Prof. Dr. T. S. Lobana Fax: 91-183-2-258820 E-Mail: tarlokslobana@yahoo.co.in [a]

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“…An intriguing phenomenon in gold chemistry which has received attention in both theoretical and experimental studies is the propensity for gold (I) atoms (Pyykko et al 1994;Assmann etal 1995;Jones et al 1995) to cluster due to the weak bonding interactions between the closed shell metal ions. Numerous gold(I) complexes with metal-metal separations of 2-78 A to 3-25 A which are less than the van der Waal's radius for gold are known to exist (Khan et al 1988;Nakamoto et al 1993;Mingos et al 1995). Other studies on multinuclear gold complexes have also shown that these attractive gold(I)-gold(I) interactions persist even in solution (Narayanaswamy et al 1993).…”

Section: The D 10 Gold (I) Systemmentioning

confidence: 99%

Tuning metal-metal distances through ligands

Abraham

Samuelson

1996

Proc. Indian Acad. Sci. (Chem. Sci.)

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Metal-metal distances in polynuclear metal complexes are often controlled by factors other than favourable metal-metal (M-M) interactions. Recently metal cluster topology has been identified as a major factor in controlling Cu~ Cu distances in tetrahedral copper clusters. The more obvious ligand control in M--M distances was shown to play a secondary role. In order to probe ways to tune metal-metal distances in clusters, a study of clusters with similar ligands around the metal has been taken up. Two broad classes were identified: Clusters in which there are two-electron two-centre bonds, and a second class where multicentre multielectron bridging is involved.Clusters held together by two-electron two-centre bonds can be analysed fairly effectively using a test electrophile like the proton. This is illustrated by analysing structures available in the literature. The sensitivity of the method to detect M-M interactions will be illustrated with examples from gold clusters where relativistic interactions cause gold d 10 -d 10 interactions to be attractive. Among the latter class Cu 3 P 6 X 2 core makes a specially interesting case study. The capping ligand X determines the extent of Cu-Cu interaction present in the cluster. Simple EHT calculations on the cluster reveal that Cu-Cu reduced overlap populations change significantly with the extent of re-donation or acceptance of the ligand.

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Synthesis of [Au(NH3)2]+ salts and the crystal structure of [Au(NH3)2]Br

Cited by 52 publications

References 2 publications

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

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

1, 9‐Dihydro‐purine‐6‐thione Derivatives of the d⁸–d¹⁰ Metal Ions (Pd^II, Pt^II, and Cu^I): Synthesis, Spectroscopy, and Structures

Tuning metal-metal distances through ligands

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Synthesis of [Au(NH3)2]+ salts and the crystal structure of [Au(NH3)2]Br

Cited by 52 publications

References 2 publications

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

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

1, 9‐Dihydro‐purine‐6‐thione Derivatives of the d8–d10 Metal Ions (PdII, PtII, and CuI): Synthesis, Spectroscopy, and Structures

Tuning metal-metal distances through ligands

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1, 9‐Dihydro‐purine‐6‐thione Derivatives of the d⁸–d¹⁰ Metal Ions (Pd^II, Pt^II, and Cu^I): Synthesis, Spectroscopy, and Structures