Copper(II) trimethylacetate complexes with 3,5-dimethylpyrazole

Denisova, T. O.; Amel’chenkova, E. V.; Pruss, I. V.; Доброхотова, Ж. В.; Fialkovskii, O. P.; Нефедов, С. Е.

doi:10.1134/s0036023606070084

Cited by 26 publications

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References 15 publications

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“…The starting materials [Co(OTf) 2 ] 2 ·6H 2 O [29], [Co(Piv) 2 ] n [30], [Cu 2 (Piv) 4 ] n [31], LiPiv [32], 4-(2-thienyl)pyrimidine (L 1 ), 4-[2,2']-(bithiophen-5-yl)-pyrimidine (L 2 ), and 4-[2,2']-bithiophen-5-yl-5-(thien-2-yl)pyrimidine (L 3 ) [8] have been prepared according to the previously reported procedures. The following solvents, MeCN, THF, CH 2 Cl 2 and 1,4-dioxane, as well as Pd(OAc) 2 (>99%, Sigma-Aldrich) were used without additional purification.…”

Section: Methods and Synthesismentioning

confidence: 99%

Synthesis and characterization of new complexes derived from 4-thienyl substituted pyrimidines

et al. 2015

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Section: Methods and Synthesismentioning

confidence: 99%

Synthesis and characterization of new complexes derived from 4-thienyl substituted pyrimidines

et al. 2015

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“…1439 (4) 4557(7) 981 (3) 82(2) C (6) 2733 (3) -208 (6) 1482 (2) 59(2) C (7) 2676(4) -1422(6) 1320(2) 79(2) C (8) 2782 (3) 202 (6) 1909 (2) 68(2) C (9) 2820 (3) 1337 (6) 1864 (2) 61(2) C (10) 2880 (5) …”

Section: (µ 4 Oh)(µ (Cf 3 ) 2 Pz) 4 (µ Oocph) 2 (µ Oh) 2 (Oh 2 )(Et 3unclassified

Formation of the unusual cluster Cu4(μ4-OH)(μ-(CF3)2pz)4(μ-OOCPh)2(μ-OH)2(OH2)(Et3NH)[O(CH2Ph)2]2 in the thermolysis of a copper μ-aqua complex with bridging pyrazolate and acetate ligands in dibenzyl ether in the presence of atmospheric oxygen

Нефедов

Kushan

Yakovleva

et al. 2012

Russ. J. Inorg. Chem.

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A room temperature reaction of cupric acetate dihydrate with 3,5 bis(trifluoromethyl)pyrazole ((CF 3 ) 2 pzH) in chloroform in the presence of triethylamine gave a complex of the formula [Cu 2 (μ (CF 3 ) 2 pz) 2 (μ OH 2 )(OC(Me)OHNEt 3 )(OH 2 )(HCCl 3 )(OOCMe)(μ OOCMe)] 2 (2). Heating of this complex at 180°C in dibenzyl ether (DBE) in air yielded the tetranuclear pyrazolate benzoate cluster Cu 4 (μ 4 OH)(μ (CF 3 ) 2 pz) 4 (μ OOCPh) 2 (μ OH) 2 (OH 2 )(Et 3 NH)[O(CH 2 Ph) 2 ] 2 . It was suggested that such complexes can be intermediates in the liquid phase oxidation of DBE with atmospheric oxygen in the presence of copper com plexes containing pyrazolate bridges.

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“…Note that these complexes may underlie the forma tion of more complex polynuclear clusters up to metal containing polymers that contain both bridging unsaturated organic fragments and transition metal atoms [1][2][3][4][5][6][7].…”

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“…Depending on the nature of the solvent, the products are binuclear lantern dimers Cu 2 (μ OOCR) 4 (Hdmpz) 2 con taining axially coordinated Hdmpz or mononuclear com plexes Cu(Hdmpz) 2 (OOCR) 2 (R = Me, Ph) the struc ture of which differs only in the intra or intermolecu lar hydrogen bonding of the oxygen atom of bridging or terminal carboxylate anion to the hydrogen atom of the pyrrole fragment of coordinated Hdmpz mole cules [6][7][8][9][10][11].…”

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confidence: 99%

“…Thus, for the binuclear pivalates M 2 (μ OOCMe 3 ) 4 (NEt 3 ) 2 containing donor tert butyl sub stituents in the carboxylate anion, reactions with 3,5 dimethylpyrazole (Hdmpz) were found to be accom panied by pyrazole deprotonation at room tempera ture in benzene to give, depending on the nature of the transition metal, pyrazolate bridged dimers M 2 (μ dmpz) 2 (Hdmpz) 2 (OOCBu t ) 2 (M = Zn, Co), a binu clear lantern dimer containing Hdmpz in the axial positions, M 2 (μ OOCBu t ) 4 (Hdmpz) 2 (M = Cu, Ni), or mononuclear complex Cu(Hdmpz) 2 (OOCBu t ) 2 [6][7][8][9][10][11][12][13][14][15][16].…”

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Deprotonation of pyrazole and its analogs by aqueous copper acetate in the presence of triethylamine

Yakovleva

Kushan

Boltacheva

et al. 2012

Russ. J. Inorg. Chem.

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Deprotonation of the pyrrole nitrogen atom of the molecules of pyrazole and its analogs by transition metal complexes gives pyrazolate bridged bi and polynuclear compounds [1][2][3][4][5]. The composition and structure of the products of these reactions are deter mined first of all by the nature of the transition metal, the donor ability of the anion present in the starting complex, and by the reaction conditions (solvent polarity, temperature, etc.).Thus, for the binuclear pivalates M 2 (μ OOCMe 3 ) 4 (NEt 3 ) 2 containing donor tert butyl sub stituents in the carboxylate anion, reactions with 3,5 dimethylpyrazole (Hdmpz) were found to be accom panied by pyrazole deprotonation at room tempera ture in benzene to give, depending on the nature of the transition metal, pyrazolate bridged dimers M 2 (μ dmpz) 2 (Hdmpz) 2 (OOCBu t ) 2 (M = Zn, Co), a binu clear lantern dimer containing Hdmpz in the axial positions, M 2 (μ OOCBu t ) 4 (Hdmpz) 2 (M = Cu, Ni), or mononuclear complex Cu(Hdmpz) 2 (OOCBu t ) 2 [6-16].Upon replacement of the bridging pivalate anion by less donor acetate or benzoate anion in the complexes of the same type containing coordinated triethylamine, analogous reactions result in pyrazolate bridged dimers Zn 2 (μ dmpz) 2 (Hdmpz) 2 (OOCR) 2 (R = Me, Ph), tri nuclear complex Co 3 (μ dmpz) 4 (Hdmpz) 2 (OOMe) 2 , or mononuclear Co(OOCPh) 2 (Hdmpz) 2 [12][13][14][15][16].In the case of copper(II) complexes, no pyrazole deprotonation takes place irrespective of the donor nature of the substituent in the carboxylate anion, as in pivalates. Depending on the nature of the solvent, the products are binuclear lantern dimers Cu 2 (μ OOCR) 4 (Hdmpz) 2 con taining axially coordinated Hdmpz or mononuclear com plexes Cu(Hdmpz) 2 (OOCR) 2 (R = Me, Ph) the struc ture of which differs only in the intra or intermolecu lar hydrogen bonding of the oxygen atom of bridging or terminal carboxylate anion to the hydrogen atom of the pyrrole fragment of coordinated Hdmpz mole cules [6][7][8][9][10][11].Deprotonation of pyrazole in mono and binuclear copper(II) pivalates occurs only during thermolysis (165°С) of the single crystals of complexes to give polynuclear pyrazolate or pivalate-pyrazolate bridg ing compounds insoluble in organic solvents [6,12].Note that these complexes may underlie the forma tion of more complex polynuclear clusters up to metal containing polymers that contain both bridging unsaturated organic fragments and transition metal atoms [1][2][3][4][5][6][7].This study considers the structural features of the products formed in reactions of aqueous copper ace tate with pyrazole (pzH), 5 methyl 3 trifluorometh ylpyrazole (MeCF 3 pzH), and 3,5 bis(trifluorome thyl)pyrazole ((CF 3 ) 2 pzH) in the presence of triethyl amine in benzene at room temperature (i.e., under conditions similar to the reactions with Hdmpz). The choice of pyrazoles was due to the fact that the intro duction of substituents into the heterocycle increases the acidity of the pyrrole hydrogen atom and, corre spondingly, decreases the pyridine a...

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Copper(II) trimethylacetate complexes with 3,5-dimethylpyrazole

Cited by 26 publications

References 15 publications

Synthesis and characterization of new complexes derived from 4-thienyl substituted pyrimidines

Synthesis and characterization of new complexes derived from 4-thienyl substituted pyrimidines

Formation of the unusual cluster Cu4(μ4-OH)(μ-(CF3)2pz)4(μ-OOCPh)2(μ-OH)2(OH2)(Et3NH)[O(CH2Ph)2]2 in the thermolysis of a copper μ-aqua complex with bridging pyrazolate and acetate ligands in dibenzyl ether in the presence of atmospheric oxygen

Deprotonation of pyrazole and its analogs by aqueous copper acetate in the presence of triethylamine

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