Structure of tris(.mu.-3,5-diphenylpyrazolato-N,N')tricopper(I). Structural comparisons with the silver(I) and gold(I) pyrazolate trimers

Raptis, Raphael G.; Fackler, John P.

doi:10.1021/ic00296a018

Cited by 112 publications

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“…[5Ϫ7] Depending on the ring substituent copper() forms a large series of derivatives: neutral 1-D polymers [Cu(pz)] ϱ for unsubstituted pyrazole, [8] cyclic trimers [Cu(pzЈ)] 3 [pzЈ ϭ 3,5-dimethyl-4-nitropyrazole (Hdmnpz), [6] 3,5-dimethylpyrazole (Hdmpz), [9] 3,5-diphenylpyrazole (Hdppz), [10] 3,4,5-trimethylpyrazole (tmpzH) [11] ] and cyclic neutral [Cu(dppz)] 4 [5] and anionic tetramers [Cu 4 -(dmnpz) 6 ]…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystallographic and Spectroscopic Studies of Dimeric Cu^I Complexes with Schiff‐Base‐Containing Triazole Ligands

2003

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New CuI complexes of the Schiff‐base‐containing triazole ligands N‐[(E)‐(4‐chlorophenyl)methylidene]‐4H‐1,2,4‐triazol‐4‐amine (ClPhtrz) and N‐[(E)‐phenylmethylidene]‐4H‐1,2,4‐triazol‐4‐amine (Phtrz) have been synthesised and characterised. Depending on the reaction conditions ClPhtrz forms two different dimeric complexes 1 and 2. X‐ray crystallography revealed that each copper centre exhibits a planar trigonal coordination in 1, while the tetrahedral coordination sphere of the copper centre in 2 is completed by a solvent molecule. In dimeric complex 3 the tetrahedral coordination of the CuI ions is formed by two monodentate and two bidentate (bridging) Phtrz ligands. Complexes 1−3 are unstable and easily lose coordinating and/or solvating acetonitrile molecules giving 4 (from 1 and 2) and 5 (from 3). On the basis of ESI MS and 1H NMR and UV/Vis spectroscopy, it was shown that dimeric complexes 1−5 do not survive upon dissolution and dissociate rapidly forming mainly a 1:2 monomeric complex, along with a minor 1:1 complex. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Section: Introductionmentioning

confidence: 99%

Synthesis, Crystallographic and Spectroscopic Studies of Dimeric Cu^I Complexes with Schiff‐Base‐Containing Triazole Ligands

2003

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“…The central nine-membered ring structure, Cu3N6, is qualitatively planar and the rings are arranged in pairs in the crystal lattice. The structure is discussed in relation to similar M(1) pyrazolate species (M = Cu, Ag, or Au) (2)(3)(4).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and X-ray crystal structure of the 3,5-dimethylpyrazolato copper(I) trimer, [Cu(pz″)]₃

Ehlert¹,

Rettig²,

Storr³

et al. 1990

Can. J. Chem.

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A moderately high-yield, high temperature synthesis of the title compound is reported. Crystals of tris [(3,5-dimethylpyrazolato-N',~2)copper(~)] are triclinic, a = 12.360(4), b = 14.637(4), c = 12.358(4) A, a = 105.29(2), P = 119.83(2), y = 93.99(3)", Z = 4 (trimers, two per asymmetric unit), space group P i . The structure was solved by heavy atom methods and was refined by full-matrix least-squares procedures to R = 0.034 andR,, = 0.038 for 3877 reflections with1 2 3a(4. The structure consists of trimeric molecules with an unusually short average Cu-N distance of 1. et Z = 4 (deux trimbes par unite asymktrique). On a affint la structure par la mtthode des atomes lourds et on l'a affinee par la mtthode des moindres canes jusqu'a des valeurs respectives de R = 0,034 et R,, = 0,038 pour 3877 reflexions avec I 3 o Q . La structure est formte de molCcules trimtres dans lesquelles la distance moyenne Cu-N, 1,852 A, est anormalement courte. Les cycles centraux a neuf chafnons de Cu3N6 sont plans a moins de 0,07 A. Des interactions Cu...Cu faibles, de distance moyenne 2,946 A, retiennent les unites de trimere par paires autour de centres de symttrie.Mots clks : trimere pyrazolato-cuivre (I), pyrazolat de cuivre (I).[Traduit par la revue]

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“…[13] Pyrazole without any substituent groups (pzH), however, forms a cyclic trinuclear Pd 6 ], under basic conditions and a mononuclear Pd II complex with four neutral pyrazole ligands, [PdA C H T U N G T R E N N U N G (pzH) 4 ]Cl 2 , under acidic conditions. The product formed under basic conditions contrasts with the case of Pt II , which forms a dimer of mononuclear complexes with intermolecular hydrogen bonding,…”

Section: Resultsmentioning

confidence: 99%

“…, [17] [PdA C H T U N G T R E N N U N G (pzH) 4 ]Cl 2 , [9] [AuClA C H T U N G T R E N N U N G (tht)] (tht = tetrahydrothiophene), [18] 3-tert-butylpyrazole (3-tBupzH), [19] and…”

Section: Methodsmentioning

confidence: 99%

“…[1] Among the various types of structures, pyrazolate and its derivatives are known to favor the formation of cyclic trinuclear complexes such as [M I 3 A C H T U N G T R E N N U N G (m-Rpz) 3 ] (M I = Cu, [2][3][4] Ag, [3,5,6] Au; [5,7] RpzH = pyrazole or substituted pyrazoles) and [M II 3 A C H T U N G T R E N N U N G (m-Rpz) 6 ] (M II = Pd, [8,9] Pt [9,10] ), the structure of the latter being similar to that of palladium(ii) acetate [Pd 3 A C H T U N G T R E N N U N G (m-OAc) 6 ]. [11] The successful partial oxidation of the platinum cyclic trimer [Pt 6 ] have been elucidated.…”

Section: Introductionmentioning

confidence: 99%

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Heteropolynuclear Palladium Complexes with Pyrazolate and Its 3‐tert‐Butyl Derivatives: The Effect of Heterometal Ions on the Rate of Isomerization

Umakoshi¹,

Kojima²,

Arikawa³

et al. 2006

Chemistry A European J

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The heteropolynuclear complexes [Pd(2)M'(2)(mu-pz)(6)] (M'=Ag (1), Au (2); pzH=pyrazole), HT-[Pd(2)M'(2)(mu-3-tBupz)(6)] (M'=Ag (3 a), Au (4 a); 3-tBupzH=3-tert-butylpyrazole), and HH-[Pd(2)Au(2)(mu-3-tBupz)(6)] (4 b) have been prepared and some of them were structurally characterized. When 3-tert-butylpyrazolate was employed as a bridging ligand, two linkage isomers (head-to-tail (HT) and head-to-head (HH)) arise from the difference in orientation of the substituent groups on the pyrazolate bridges between the two Pd atoms. (1)H NMR spectroscopy has been used to identify and to follow the reversible stereochemical rearrangement of the HH isomer of [Pd(2)Ag(2)(mu-3-tBupz)(6)] (3 b) to form the HT isomer 3 a in CDCl(3) and the HT isomer of [Pd(2)Au(2)(mu-3-tBupz)(6)] (4 a) to form the HH isomer 4 b in C(6)D(6). Kinetic studies of the reaction have established the rate law to be -d(HH)/dt=d(HT)/dt=k(2)[HH]-k(1)[HT] for 3 b and -d(HT)/dt=d(HH)/dt=k(1)[HT]-k(2)[HH] for 4 a, where k(1) and k(2) denote the rate of isomerization from the HT to the HH isomer and that from the HH to the HT isomer, respectively. For typical runs at 50 degrees C in C(6)D(6), k(1)=13.8x10(-5) s(-1), k(2)=18.6x10(-5) s(-1), and K(eq)=k(2)/k(1)=1.24 for 3 b, and k(1)=1.26x10(-5) s(-1), k(2)=3.52x10(-5) s(-1), and K(eq)=k(1)/k(2)=0.36 for 4 a. Temperature-dependent rate measurements reveal DeltaH(not equal) and DeltaS(not equal) to be 100(1) kJ mol(-1) and 0(3) J mol(-1) K(-1) for 3 b and 112(5) kJ mol(-1) and 20(17) J mol(-1) K(-1) for 4 a, respectively. The rate of isomerization is essentially unaffected by the concentration of the complex or by the presence of neutral bridging ligands. These data and observations imply that the isomerization involves an intramolecular exchange process.

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Structure of tris(.mu.-3,5-diphenylpyrazolato-N,N')tricopper(I). Structural comparisons with the silver(I) and gold(I) pyrazolate trimers

Cited by 112 publications

References 1 publication

Synthesis, Crystallographic and Spectroscopic Studies of Dimeric Cu^I Complexes with Schiff‐Base‐Containing Triazole Ligands

Synthesis, Crystallographic and Spectroscopic Studies of Dimeric Cu^I Complexes with Schiff‐Base‐Containing Triazole Ligands

Synthesis and X-ray crystal structure of the 3,5-dimethylpyrazolato copper(I) trimer, [Cu(pz″)]₃

Heteropolynuclear Palladium Complexes with Pyrazolate and Its 3‐tert‐Butyl Derivatives: The Effect of Heterometal Ions on the Rate of Isomerization

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Structure of tris(.mu.-3,5-diphenylpyrazolato-N,N')tricopper(I). Structural comparisons with the silver(I) and gold(I) pyrazolate trimers

Cited by 112 publications

References 1 publication

Synthesis, Crystallographic and Spectroscopic Studies of Dimeric CuI Complexes with Schiff‐Base‐Containing Triazole Ligands

Synthesis, Crystallographic and Spectroscopic Studies of Dimeric CuI Complexes with Schiff‐Base‐Containing Triazole Ligands

Synthesis and X-ray crystal structure of the 3,5-dimethylpyrazolato copper(I) trimer, [Cu(pz″)]3

Heteropolynuclear Palladium Complexes with Pyrazolate and Its 3‐tert‐Butyl Derivatives: The Effect of Heterometal Ions on the Rate of Isomerization

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Synthesis, Crystallographic and Spectroscopic Studies of Dimeric Cu^I Complexes with Schiff‐Base‐Containing Triazole Ligands

Synthesis, Crystallographic and Spectroscopic Studies of Dimeric Cu^I Complexes with Schiff‐Base‐Containing Triazole Ligands

Synthesis and X-ray crystal structure of the 3,5-dimethylpyrazolato copper(I) trimer, [Cu(pz″)]₃