Co-ordinative versatility of 3,5-bis(2-pyridyl)pyrazole in silver and copper compounds

Munakata, Megumu; Wu, Liang; Yamamoto, Mikiko; Kuroda–Sowa, Takayoshi; Maekawa, Masahiko; Kawata, Satoshi; Kitagawa, Susumu

doi:10.1039/dt9950004099

Cited by 54 publications

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“…± 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].…”

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Copper Complexes with New Pyridylpyrazole Based Ligands

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Heras

et al. 2002

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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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“…The best planes formed by the atoms in each of the aromatic rings Table 1. Selected Bond Distances [ä] and Angles [8] for the Ligands L 1 and L 2 (1) 110.0(2) (1) 110.7 (2) were calculated, and the dihedral angles between adjacent rings are discussed below.…”

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Copper Complexes with New Pyridylpyrazole Based Ligands

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“…Data collection: RAPID-AUTO (Rigaku, 2002); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure. (Munakata et al, 1995;Du et al, 2005;Ishikawa et al, 2010). The dinuclear complexes show the structure where two bpypzions are bridging two metal ions with the axial coordination sites.…”

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“…For metal complexes of 3,5-bis(2-pyridyl)pyrazole, see: Munakata et al (1995); Nakano et al (2004); Du et al (2005); Yoneda, Adachi, Hayami et al (2006); Yoneda, Adachi, Nishio et al (2006); Ishikawa et al (2008Ishikawa et al ( , 2010. For an example of a coordinated hydrogensulfate ion, see: Dragancea et al (2008).…”

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Bis[μ-3,5-bis(2-pyridyl)pyrazolato]bis(hydrogensulfato)dicopper(II) methanol disolvate

et al. 2011

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The title compound, [Cu2(C13H9N4)2(HSO4)2]·2CH3OH, consists of discrete centrosymmetric dinuclear complex molecules and methanol solvent molecules. The CuII atom shows a square-pyramidal coordination geometry and is bonded to four N atoms of the two bis-chelating 3,5-bis(2-pyridyl)pyrazolate ions (bpypz−) and one O atom of the hydrogensulfate ion. The bpypz− ligands in the complex molecule are virtually coplanar [dihedral angle between the mean ligand planes = 0.000(1)°] with the CuII atom deviating in opposite directions from their best plane by 0.2080 (12) Å. π–π stacking interactions between the pyridyl and pyrazole rings [centroid–centroid distance = 3.391 (3) Å] and strong O—H⋯O hydrogen bonds between the hydrogensulfate ligands and the methanol molecules assemble the molecules into a one-dimensional polymeric structure extending along the a axis. The methanol molecule acts both as an accepter and a donor in the hydrogen bonding.

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“…Used alone or in combination with an additional ancillary ligand, the Hbpp ligand has lead to the isolation of various homo‐ and hetero‐bimetallic complexes with several transition metal ions (Ru 2+ , Ni 2+ , Cu 2+ , Fe 2+ , Co 2+ , Mn 2+ , Cr 3+ , Ln 3+ , Zn 2+ ). If dinuclear are the most common compounds, [21,24–46] few examples of tri‐, [47] tetra‐ [48] and pentanuclear have been described as well. The pentanuclear complexes, synthetized at high temperature by reacting the deprotonated bpp − ligand with the first‐row transition metal ion Fe 2+ , Mn 2+ , Ni 2+ , Cu 2+ , Zn 2+ or Co 2+ , feature a remarkable bis(triple‐helical) architecture in which the five metal ions are arranged in a trigonal bipyramidal topology with two axial {M( μ ‐bpp) 3 } units connecting a central μ 3 ‐oxo or hydroxo trinuclear core {M 3 ( μ 3 ‐X)} (X=O or OH) (Scheme 1).…”

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Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the Ni^II₅ and Ni^INi^II₄ Redox States

et al. 2021

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We previously reported the multireversible redox behavior of bis(triple‐helicate) pentanuclear complexes of the type [{M(μ‐bpp)3}2M(μ3‐X)]n+ (M=Mn, Fe with X=O and Co with X=OH) with rigid tetradentate binucleating 3,5‐bis(pyridine‐2‐yl)pyrazole (bpp−) ligand. In this article, we focus on the nickel derivative of this family, [{NiII(μ‐bpp)3}2NiII3(μ‐OH)]3+ (13+), which exhibits up to five reversible or quasi‐reversible one‐electron waves in CH3CN solution. The two one‐electron oxidized species as well as the one‐electron reduced species with respective compositions of 4NiII1NiIII (14+), 3NiII2NiIII (15+) and 1NiI4NiII (12+), were quantitatively generated by bulk electrolyses and spectroscopically characterized highlighting the high stability of this family of complexes in several redox states. In addition to the initial complex 13+, the mixed‐valence 12+ was also successfully characterized by single‐crystal X‐ray diffraction, allowing to locate the sites of successive reversible one‐electron events. 12+ is an unusual example of a multinuclear complex including the low‐valent Ni(I) state.

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Co-ordinative versatility of 3,5-bis(2-pyridyl)pyrazole in silver and copper compounds

Cited by 54 publications

References 19 publications

Copper Complexes with New Pyridylpyrazole Based Ligands

Copper Complexes with New Pyridylpyrazole Based Ligands

Bis[μ-3,5-bis(2-pyridyl)pyrazolato]bis(hydrogensulfato)dicopper(II) methanol disolvate

Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the Ni^II₅ and Ni^INi^II₄ Redox States

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Co-ordinative versatility of 3,5-bis(2-pyridyl)pyrazole in silver and copper compounds

Cited by 54 publications

References 19 publications

Copper Complexes with New Pyridylpyrazole Based Ligands

Copper Complexes with New Pyridylpyrazole Based Ligands

Bis[μ-3,5-bis(2-pyridyl)pyrazolato]bis(hydrogensulfato)dicopper(II) methanol disolvate

Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the NiII5 and NiINiII4 Redox States

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Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the Ni^II₅ and Ni^INi^II₄ Redox States