The structure of [Au-μ-{3,5-(C6H5)2C3HN2}]3Cl2: a trinuclear mixed-valence gold pyrazolate complex

Raptis, Raphael G.; Murray, H. H.; Fackler, John P.

doi:10.1107/s0108270188001830

Cited by 13 publications

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“…The core of the molecule is formed by three gold atoms bridged through three exobidentate pyrazolate groups, forming a nine-membered ring (Figure ). This gold−pyrazolate macrocycle is not uncommon in the chemistry of group 11 metals; similar situations have been reported for the related (carbenato)gold(I) complex [Au{C(OEt)N(C 6 H 4 Me)}] 3 or the (pyrazolato)gold(I) complexes [Au(μ-3,5-(CF 3 ) 2 Pz)] 3 10b and [Au(μ- 3,5-Ph 2 Pz)] 3 , for the heterovalent Au(I)/Au(III) compounds [{Au(μ-3,5-Ph 2 Pz)} 3 Cl 2 ] and [{Au(μ-3,5-Ph 2 -4-ClPz)} 3 Cl 2 ], , and for the closely related silver(I) analogue [Ag(μ-3,5-Ph 2 Pz)] 3 . In 5 , as in all the previous structures (except [Au(μ-3,5-Ph 2 Pz)] 3 , which exhibits intramolecular crystallographically imposed symmetry), the metallacycle is not strictly planar, but slightly irregular and puckered.…”

Section: Resultssupporting

confidence: 72%

“…The observed N−Au lengths range between 1.99(2) and 2.07(2) Å, with mean values of 2.01 and 2.03(1) Å for both independent molecules. These values are longer than those reported for the CF 3 analogue,10b 1.93(3) Å, but statistically indistinguishable from the Au−N bond distances described in complexes containing phenyl-substituted pyrazolate ligands (range 1.978(9)−2.05(2) Å). ,, The pyrazolate rings and the phenyl groups maintain strict planarity and do not deserve further comment.…”

Section: Resultsmentioning

confidence: 50%

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(Pyrazolato)gold Complexes Showing Room-Temperature Columnar Mesophases. Synthesis, Properties, and Structural Characterization

et al. 1998

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Mesogenic (pyrazolato)gold complexes of formula [Au(pz)]3 (pz = 3,5-bis(3‘,4‘-di-n-decyloxyphenyl)pyrazole (1), 3-(3‘,4‘,5‘-tri-n-decyloxyphenyl)-5-(3‘‘,4‘‘-di-n-decyloxyphenyl)pyrazole (2), 3-(2‘,3‘,4‘-tri-n-decyloxyphenyl)-5-(3‘‘,4‘‘,5‘‘-tri-n-decyloxyphenyl)pyrazole (3), 3,5-bis(3‘,4‘,5‘-tri-n-decyloxyphenyl)pyrazole (4)) have been prepared by reaction of the potassium salts of the nonmesogenic pyrazolate ligands with [AuCl(tht)] (tht = tetrahydrothiophene) in a 1:1 molar ratio. All these compounds show columnar mesophases that remain stable, at room temperature, for long periods of time. The formation of isomers for the nonsymmetrical derivativesdetected by spectroscopic studiesare suggested to be responsible for the subtle changes observed in the transition temperatures. Powder X-ray diffraction measurements show clearly that the supramolecular columnar arrangement appears in the crystalline solids as well as in the mesomorphic phase. An analogue of the mesogenic trinuclear complexes 1 − 4, having a methoxy group at the phenyl substituents of the pyrazolate ligands, [Au{3,5-(MeOPh)2Pz}]3 (5), has been synthesized and characterized by an X-ray single-crystal diffraction experiment. The molecular structure of 5 is based on a nine-membered metallacycle core. The whole molecule exhibits a rough planarity that favors a crystalline structure formed from columnar arrangements of trinuclear complexes. A simple and clear relationship could be established between the solid-state crystal structure of 5 and the X-ray-deduced structure of the mesophases.

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Section: Resultssupporting

confidence: 72%

Section: Resultsmentioning

confidence: 50%

(Pyrazolato)gold Complexes Showing Room-Temperature Columnar Mesophases. Synthesis, Properties, and Structural Characterization

et al. 1998

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“…The reaction of Au 3 (3,5-Ph 2 Pz) 3 with aqua regia afforded the partially oxidized product Au 3 (3,5-Ph 2 Pz) 3 Cl 2 , in which one of the three Au(I) ions was oxidized to Au(III) . This mixed-valence Au(I) 2 Au(III) CTC can also be synthesized by the direct reaction of Au(pyridine)Cl 3 with Na(3,5-Ph 2 Pz) in a THF solution . In 2002, Raptis et al reported the X-ray crystal structures of Au(I)Au(III) 2 and Au(III) 3 species from the oxidation reactions of Au 3 (3,5-Me 2 Pz) 3 with aqua regia …”

Section: Synthesis and Reactivitymentioning

confidence: 99%

Coinage-Metal-Based Cyclic Trinuclear Complexes with Metal–Metal Interactions: Theories to Experiments and Structures to Functions

et al. 2020

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Among the d 10 coinage metal complexes, cyclic trinuclear complexes (CTCs) or trinuclear metallocycles with intratrimer metal−metal interactions are fascinating and important metal−organic or organometallic π-acids/bases. Each CTC of characteristic planar or near-planar trimetal nine-membered rings consists of Au(I)/Ag(I)/Cu(I) cations that linearly coordinate with N and/or C atoms in ditopic anionic bridging ligands. Since the first discovery of Au(I) CTC in the 1970s, research of CTCs has involved several fundamental areas, including noncovalent and metallophilic interaction, excimer/exciplex, acid−base chemistry, metalloaromaticity, supramolecular assemblies, and host/guest chemistry. These allow CTCs to be embraced in a wide range of innovative potential applications that include chemical sensing, semiconducting, gas and liquid adsorption/separation, catalysis, full-color display, and solid-state lighting. This review aims to provide a historic and comprehensive summary on CTCs and their extension to higher nuclearity complexes and coordination polymers from the perspectives of synthesis, structure, theoretical insight, and potential applications.

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“…These kinds of ligands have a proven ability to hold metal atoms in close proximity while permitting a wide range of intermetallic separations, being useful in the synthesis of shape-persistent macrocycles, such as the homonuclear [M I A C H T U N G T R E N N U N G (m-Rpz)] 3 (M = Cu, [36][37][38][39][40][41][42] Ag, [37,38,43,44] Au; [43,[45][46][47][48][49][50] Rpz = pyrazolate or substituted pyrazolate) or [M II 3 A C H T U N G T R E N N U N G (m-Rpz) 6 ] (M II = Pd [51,52] Pt [52,53] ) as the heteronuclear clusters [Pd 2 M 2 A C H T U N G T R E N N U N G (m-Rpz) 6 ] (M = Cu, Ag, Au), [52,54] and [M 2 M' 4 A C H T U N G T R E N N U N G (m-Rpz) 8 ] (M = Pd, Pt; M' = Cu, Ag). [52,55] Apart from the interest arising from their structural diversity, some of these pyrazolate bridging complexes have also been shown to be excellent systems for examining metallophilic interactions [49,[56][57][58][59][60][61][62] and as luminescent materials.…”

Section: ) Lm'ct Transitions P-a C H T U N G T R E N N U N G (Dmpz)!mmentioning

confidence: 99%

Homo‐ and Heteropolynuclear Platinum Complexes Stabilized by Dimethylpyrazolato and Alkynyl Bridging Ligands: Synthesis, Structures, and Luminescence

Forniés

Fuertes

Martín

et al. 2006

Chemistry A European J

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This work describes the synthesis of cis-[Pt(C[triple bond]CPh)2(Hdmpz)2] (1) and its use as a precursor for the preparation of homo- and heteropolynuclear complexes. Double deprotonation of compound 1 with readily available M(I) (M = Cu, Ag, Au) or M(II) (M = Pd, Pt) species affords the discrete hexanuclear clusters [{PtM2(mu-C[triple bond]CPh)2(mu-dmpz)(2)}(2)] [M = Cu (2), Ag (3), Au (4)], in which both "Pt(C[triple bond]CPh)2(dmpz)(2)" fragments are connected by four d(10) metal centers, and are stabilized by alkynyl and dimethylpyrazolate bridging ligands, or the trinuclear complexes [Pt(mu-C[triple bond]CPh)2(mu-dmpz)(2){M(C/\P)}2] (M = Pd (5), Pt (6); C/\P = CH(2)-C(6)H(4)-P(o-tolyl)2-kappaC,P), respectively. The X-ray structures of complexes 1-4 and 6 are reported. The X-ray structure of the platinum-copper derivative 2 shows that all copper centers exhibit similar local geometry being linearly coordinated to a nitrogen atom and eta(2) to one alkynyl fragment. However in the related platinum-silver (3) and platinum-gold (4) derivatives the silver and gold atoms present three different coordination environments. The complexes have been studied by absorption and emission spectroscopy. The hexanuclear complexes exhibit bright luminescence in the solid state and in fluid solution (except 4 in the solid state at 298 K). Dual long-lived emission is observed, being clearly resolved in low-temperature rigid media. The low-energy emission is ascribed to MLM'CT Pt(d)/pi(C[triple bond]CPh)-->Pt(p(z))/M'(sp)/pi*(C[triple bond]CPh) modified by metal-metal interactions whereas the high-energy emission is tentatively attributed to an emissive state derived from dimethylpyrazolate-to-metal (d(10)) LM'CT transitions pi(dmpz)-->M'(d(10)).

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The structure of [Au-μ-{3,5-(C₆H₅)₂C₃HN₂}]₃Cl₂: a trinuclear mixed-valence gold pyrazolate complex

Abstract: Abstract.Tris-/~-(3,5-diphenyl-1-pyrazolyl-N,N')-di-

Cited by 13 publications

References 5 publications

(Pyrazolato)gold Complexes Showing Room-Temperature Columnar Mesophases. Synthesis, Properties, and Structural Characterization

(Pyrazolato)gold Complexes Showing Room-Temperature Columnar Mesophases. Synthesis, Properties, and Structural Characterization

Coinage-Metal-Based Cyclic Trinuclear Complexes with Metal–Metal Interactions: Theories to Experiments and Structures to Functions

Homo‐ and Heteropolynuclear Platinum Complexes Stabilized by Dimethylpyrazolato and Alkynyl Bridging Ligands: Synthesis, Structures, and Luminescence

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