Copper(I) reoxygenation products: the structures of di-μ-hydroxy-bis(di-2-pyridylamine)bis(tetrafluoroborato)dicopper(II) and μ-aqua-di-μ-hydroxy-bis(di-2-pyridylamine)dicopper(II) dichloride dihydrate

Wu, Liang-Ping; Keniry, M. E.; Hathaway, B. J.

doi:10.1107/s0108270191008703

Cited by 19 publications

(3 citation statements)

References 7 publications

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“…1 H-NMR: 6.77 (s, HÀC(4)(pz)); 6.96 (d, 3 J 9, 2 H m (C 6 H 4 )); 7.1 ± 7.4 (m, 15 H, C 6 H 4 , C 6 H 5 O, HÀC(5')(py)); 7.61 (−d×, HÀC(3')(py)); 7.79 (−t×, HÀC(4')(py)); 7.91 (d, 3 J 9, 2 H o (C 6 H 4 )); 8.41 (−d×, HÀC(6')(py)). 13 f and w f and w Data collected ( À 12, À 5, À 23) to (19,9,22) ( À 18, À 6, À 20) to (17,6,34) Crystal-Structure Determinations. Suitable crystals for X-ray experiments of compounds L 1 , L 2 , 1a, 1b, 2a, and 3 were obtained as described above (synthetic methods), and those of bis[3,5-bis(4-butoxyphenyl)-1-(pyridin-2-yl-kN)-1H-pyrazole-kN 2 ]chlorocopper(II) hexafluorophosphate (4) were formed by aereal oxidation of a CH 2 Cl 2 soln.…”

Section: Experimental Partmentioning

confidence: 99%

Copper Complexes with New Pyridylpyrazole Based Ligands

Campo

Cano

Heras

et al. 2002

HCA

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We report the synthesis, characterization, and crystal structures of new ligands of the pyridinylpyrazole type, i.e., 3,5-bis(4-butoxyphenyl)-1-(pyridin-2-yl)-1H-pyrazole (L 1 ) and 3,5-bis(4-phenoxyphenyl)-1-(pyridin-2-yl)-1H-pyrazole (L 2 ) (Scheme 1), and the study of their coordination behavior towards Cu I and Cu II . The versatility of this type of ligand, which can give access to different coordination spheres about the metal center, depending on the nature of the copper starting material used in the preparation of the complexes (Scheme 2), is illustrated. Thus, pseudo-tetrahedral Cu I as well as six-coordinated tetragonal and distorted tetragonal pyramidal Cu II derivatives were obtained for [Cu(L) 2 ]PF 6 , [Cu(Cl) 2 (L) 2 ] (L L 1 , L 2 ), and [Cu(Cl)(L 1 ) 2 ]PF 6 , respectively. We also present a crystallographic support of a distorted octahedral cis-bis(tetrafluoroboratokF)copper(II) compound found for [Cu(BF 4 ) 2 (L 1 ) 2 ] (3).Introduction. ± Chelating ligands based on the pyrazole ring have been developed extensively in the last years [1] [2]. Most of the actual work deals with pyrazole rings bearing one or two bulky N-heterocycle substituents at the 3 and/or 5 position, as this type of ligand often produces multimetallic compounds [1 ± 6]. By constrast, related 1-substituted pyrazoles with heterocyclic substituents, which can act as bidentate ligands, have received less attention [7 ± 9]. They are, however, versatile ligands whose coordinative abilities could be influenced by the nature of additional substituents at the 3 and/or 5 position of the pyrazole ring.In this context, it is interesting to note that a (pyridinylpyrazole)-type ligand such as 5-methyl-1-(pyridin-2-yl)-1H-pyrazole-3-carboxamide (L c ) formed Cu II compounds of formula [CuX 2 (L c ) 2 ¥ H 2 O] (X Cl, Br, NO 3 , ClO 4 ) with a distorted octahedral geometry [10]. To achieve that, one of the two L c ligands acted in a N,N'-bidentate and the other in a N,N',O-tridentate fashion with the amide O-atom participating in the latter case and the sixth apical coordination site being occupied by a H 2 O molecule or a X counterion [10]. However, a related [Cu(La) 2 ] 2 complex with the 3-(2,5-dimethoxyphenyl)-1-(pyridin-2-yl)-1H-pyrazole (L a ) ligand showed a tetrahedrically distorted planar geometry in which, in addition to the CuN 4 core, CuÀO interactions with the MeO groups of each ligand were observed [11].From these results, it appears that O-containing substituents at the 3 and 5 positions of the pyrazole ring of the pyridinylpyrazole ligands can play an important role in the stereochemistry of the copper derivatives.Following these precedents, we are now interested in using O-containing 3,5-disubstituted pyridinylpyrazole ligands in metal complexes to produce different geometries that might allow access to certain types of supramolecular arrangements.

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Section: Experimental Partmentioning

confidence: 99%

Copper Complexes with New Pyridylpyrazole Based Ligands

Campo

Cano

Heras

et al. 2002

HCA

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“…Prior to this work, the {M 4 ( μ -OH) 4 } 4+ structural motif of 4 was not observed with copper(II), although it was characterized with nickel(II), and similar structures of iron(III) with oxo, rather than hydroxo, ligands have also been encountered . The formation of tetranuclear 4 (OTs) 4 rather than a bis( μ -hydroxo)dicopper(II) compound probably results because the geometric restrictions imposed by the bridging phthalazine unit disfavor the {Cu 2 ( μ -OH) 2 } 2+ core found in other complexes. − …”

Section: Resultsmentioning

confidence: 99%

“…46 The formation of tetranuclear 4(OTs) 4 rather than a bis(µ-hydroxo)dicopper(II) compound probably results because the geometric restrictions imposed by the bridging phthalazine unit disfavor the {Cu 2 (µ-OH) 2 } 2+ core found in other complexes. [47][48][49][50] Preparation and Crystal Structure of a Bridging Vinylpyridine Dicopper(I) Derivative. Complex 5(OTf) 2 was synthesized in high yield (86%) by the reaction of 1(OTf) 2 with vpy.…”

Section: Synthesis Of Amentioning

confidence: 99%

Synthesis and Characterization of Cu₂(I,I), Cu₂(I,II), and Cu₂(II,II) Compounds Supported by Two Phthalazine-Based Ligands: Influence of a Hydrophobic Pocket

et al. 2004

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The copper coordination chemistry of two phthalazine-based ligands of differing steric bulk was investigated. A family of dinuclear complexes were prepared from reactions of [Cu(2)(bdptz)(MeCN)(2)](OTf)(2), 1(OTf)(2), where bdptz = 1,4-bis(2,2'-dipyridylmethyl)phthalazine. Treatment of 1(OTf)(2) with NaO(2)CCH(3) afforded the class I mixed-valent compound [Cu(2)(bdptz)(2)](OTf)(3), 2(OTf)(3), by disproportionation of Cu(I). Compound 2(OTf)(3) displays an electron paramagnetic resonance spectrum, with g( parallel ) = 2.25 (A( parallel ) = 169 G) and g( perpendicular ) = 2.06, and exhibits a reversible redox wave at -452 mV versus Cp(2)Fe(+)/Cp(2)Fe. The complex [Cu(2)(bdptz)(micro-OH)(MeCN)(2)](OTf)(3), 3(OTf)(3), was prepared by chemical oxidation of 1 with AgOTf, and exposure of 1 to dioxygen afforded [Cu(2)(bdptz)(micro-OH)(2)](2)(OTs)(4), 4(OTs)(4), which can also be obtained directly from [Cu(H(2)O)(6)](OTs)(2). In compound [Cu(2)(bdptz)(micro-vpy)](OTf)(2), 5(OTf)(2), where vpy = 2-vinylpyridine, the vpy ligand bridges the two Cu(I) centers by using both its pyridine nitrogen and the olefin as donor functionalities. The sterically hindered compounds [Cu(2)(Ph(4)bdptz)(MeCN)(2)](OTf)(2), 6(OTf)(2), and [Cu(2)(Ph(4)bdptz)(micro-O(2)CCH(3))](OTf), 7(OTf), were also synthesized, where Ph(4)bdptz = 1,4-bis[bis(6-phenyl-2-pyridyl)methyl]phthalazine. Complexes 1-7 were characterized structurally by X-ray crystallography. In 6 and 7, the four phenyl rings form a hydrophobic pocket that houses the acetonitrile and acetate ligands. Complex 6 displays two reversible redox waves with E(1/2) values of +41 and +516 mV versus Cp(2)Fe(+)/Cp(2)Fe. Analysis of oxygenated solutions of 6 by electrospray ionization mass spectrometry reveals probable aromatic hydroxylation of the Ph(4)bdptz ligand. The different chemical and electrochemical behavior of 1 versus 6 highlights the influence of a hydrophobic binding pocket on the stability and reactivity of the dicopper(I) centers.

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A Unique Dinuclear CuII Compound with Two Phase Transitions Clearly Visible from Thermal and Magnetic Behaviour; Synthesis, Magnetism and X-ray Structures at Three Temperatures of Bis(di-2-pyridylamine)bis(μ-hydroxo)bis(μ-perchlorato-O,O)dicopper(II)

Youngme

Albada

Kooijman

et al. 2002

Eur. J. Inorg. Chem.

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A new compound, [Cu(dpyam)(OH)]2(ClO4)2 (dpyam = di‐2‐pyridylamine) is studied in detail and characterised by magnetic susceptibility and heat capacity measurements. This unique compound exhibits two phase transitions at 192 and 116 K. To obtain more insight into the origin of this transition, X‐ray crystal structures at 3 different temperatures, below (1A, 110 K), between (1B, 150 K) and above (1C, 200 K) the transitions are measured. The structure consists of a dinuclear CuII unit with two bridging hydroxo groups and with two ligands bound to each copper atom via N, while the axial sites are occupied by oxygen atoms of bridging perchlorate anions, providing a distorted tetragonal environment with a Cu−Cu distance which varies from 2.9328(6) to 2.9633(6) Å, and a Cu−O−Cu angle which varies from 99.00(9) to 100.53(9)°. In all three structures, the Cu2O2L2 unit does not change significantly. The only changes involve the position of the perchlorate anions and their H bonds with the bridging OH groups. These anions have slightly different positions at different temperatures and appear to be the major origin of the crystallographic phase‐transitions. Fitting the magnetic susceptibility measurements revealed a singlet‐triplet separation (J) of −37.2 cm−1 (antiferromagnetic), in the temperature ranges 275−190 K and 115−50 K. In the range 190−115 K a best fit, albeit inaccurate, of 29.3 cm−1 for J (ferromagnetic) is found. A small magnetic hysteresis of 0.5 K has been observed in the phase transition at 116 K. The heat capacity measurements have confirmed the transitions and the excess entropy (ΔS) and enthalpy (ΔH) have been calculated as 4.9 and 2.0 J K−1 mol−1 for ΔS (for 192.3 K and 116.4 K, respectively), and 0.96 and 0.25 kJ mol−1 for ΔH (for 192.3 K and 116.4 K, respectively). (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Copper(I) reoxygenation products: the structures of di-μ-hydroxy-bis(di-2-pyridylamine)bis(tetrafluoroborato)dicopper(II) and μ-aqua-di-μ-hydroxy-bis(di-2-pyridylamine)dicopper(II) dichloride dihydrate

Cited by 19 publications

References 7 publications

Copper Complexes with New Pyridylpyrazole Based Ligands

Copper Complexes with New Pyridylpyrazole Based Ligands

Synthesis and Characterization of Cu₂(I,I), Cu₂(I,II), and Cu₂(II,II) Compounds Supported by Two Phthalazine-Based Ligands: Influence of a Hydrophobic Pocket

A Unique Dinuclear CuII Compound with Two Phase Transitions Clearly Visible from Thermal and Magnetic Behaviour; Synthesis, Magnetism and X-ray Structures at Three Temperatures of Bis(di-2-pyridylamine)bis(μ-hydroxo)bis(μ-perchlorato-O,O)dicopper(II)

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Copper(I) reoxygenation products: the structures of di-μ-hydroxy-bis(di-2-pyridylamine)bis(tetrafluoroborato)dicopper(II) and μ-aqua-di-μ-hydroxy-bis(di-2-pyridylamine)dicopper(II) dichloride dihydrate

Cited by 19 publications

References 7 publications

Copper Complexes with New Pyridylpyrazole Based Ligands

Copper Complexes with New Pyridylpyrazole Based Ligands

Synthesis and Characterization of Cu2(I,I), Cu2(I,II), and Cu2(II,II) Compounds Supported by Two Phthalazine-Based Ligands: Influence of a Hydrophobic Pocket

A Unique Dinuclear CuII Compound with Two Phase Transitions Clearly Visible from Thermal and Magnetic Behaviour; Synthesis, Magnetism and X-ray Structures at Three Temperatures of Bis(di-2-pyridylamine)bis(μ-hydroxo)bis(μ-perchlorato-O,O)dicopper(II)

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Synthesis and Characterization of Cu₂(I,I), Cu₂(I,II), and Cu₂(II,II) Compounds Supported by Two Phthalazine-Based Ligands: Influence of a Hydrophobic Pocket