One-Dimensional Polymers Containing Strictly Collinear Metal Ions:  Synthesis and XRPD Characterization of Homoleptic Binary Metal Pyrazolates

Masciocchi, Norberto; Ardizzoia, G. Attilio; Brenna, Stefano; LaMonica, Girolamo; Maspero, Angelo; Galli, Simona; Sironi, Angelo

doi:10.1021/ic025821e

Cited by 67 publications

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References 45 publications

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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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“…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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“…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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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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confidence: 99%

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confidence: 99%

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confidence: 99%

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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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“…Coordination of pyrazole and its analogues to a transition metal atom increases the acidity of the pyr role fragment of the heterocycle, and such complexes can be used in the design of homo and heterometallic pyrazolate bridged complexes and clusters [1][2][3][4][5][6][7].…”

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Synthesis and structure of palladium triflates with coordinated 3,5-dimethylpyrazole

Uvarova

Kushan

Нефедов

2012

Russ. J. Inorg. Chem.

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We discovered that reacting Pd 3 (μ OOCMe) 3 with two moles of trifluoromethanesulfonic acid (Hotf) and then with four moles of 3,5 dimethylpyrazole (Hdmpz) in acetonitrile and benzene produces, in high yields, [Pd(Hdmpz) 4 ](otf) 2 and Pd(Hdmpz) 4 (HOOCMe) 2 (otf) 2 , respectively. Reacting PhenPd(OOCMe) 2 with Hotf in MeCN yields PhenPd(NCMe) 2 (otf) 2 , where labile acetonitrile molecules are substituted by Hdmpz under mild conditions to form PhenPd(Hdmpz) 2 (otf) 2 . The structures of complexes have been solved on the basis of X ray crystallography data.

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Self‐Assembly of Coordination Compounds: Design Principles

Álvarez

Ruiz

2012

Supramolecular Chemistry

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The terminology and basic concepts of coordination chemistry are presented, in view of their potential application in the design of supramolecular systems based on transition metals. We describe the main features of the metal ions, mostly in relation to atomic size and oxidation state, and those of the ligands, such as denticity, topology, and flexibility. Polyhedra as stereochemical descriptors and the relationships of nested polyhedra are analyzed. The dependence of stereochemical preferences of the most common six‐ and four‐coordinate metal centers on the electron configuration is systematically studied, and a brief description of the common stereochemistries for other coordination numbers is presented. Finally, basic criteria for understanding the choice of coordination number by a particular combination of metal and ligands are discussed, and ways to describe the stereochemistries of coordination centers with ill‐defined coordination numbers are proposed.

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One-Dimensional Polymers Containing Strictly Collinear Metal Ions: Synthesis and XRPD Characterization of Homoleptic Binary Metal Pyrazolates

Cited by 67 publications

References 45 publications

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

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

Synthesis and structure of palladium triflates with coordinated 3,5-dimethylpyrazole

Self‐Assembly of Coordination Compounds: Design Principles

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