Polynuclear transition metal complexes of metal⋯metal-bridging compartmental pyrazolate ligands

Klingele, Julia; Dechert, Sebastian; Meyer, Franc

doi:10.1016/j.ccr.2009.03.026

Cited by 217 publications

(163 citation statements)

References 176 publications

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“…We have previously shown pyrazoles with chelating side arms to be versatile bridging ligands in diand multinuclear transition-metal complexes. [6] Consequently, one of the goals of the work was to bind two metals in close proximity in these highly preorganized binding pockets. [7] We are not the first to conceive the Siamese-twin porphyrin structure.…”

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Siamese‐Twin Porphyrin: A Pyrazole‐Based Expanded Porphyrin Providing a Bimetallic Cavity

et al. 2011

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Porphyrins joined at the hip: A long‐sought expanded porphyrin has been synthesized that contains two porphyrin‐like {N4} binding sites linked by two bridging pyrazole units. Structural and spectroscopic evidence indicates the absence of macrocyclic aromatic π conjugation. In its dicopper complex (see picture) the two magnetic CuII orbitals are nearly orthogonal, and consequently this represents the first ferromagnetically coupled doubly pyrazolato‐bridged complex.

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“…[16] The Cu···Cu distance of 3.88 is well within the range of metal-metal separations in pyrazolate-bridged binuclear systems (3.5-4.0 ). [6,17] In (aromatic) metalloporphyrins, the neighboring C a À N and C a ÀC meso bonds are equal in length. The corresponding bond lengths in 9·Cu 2 differ, however.…”

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Siamese‐Twin Porphyrin: A Pyrazole‐Based Expanded Porphyrin Providing a Bimetallic Cavity

et al. 2011

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“…For metal complexes of 3,5-bis(2-pyridyl)pyrazole, see: Klingele et al (2009) ;Yoneda, Adachi, Hayami et al (2006); Yoneda, Adachi, Nishio et al (2006); Ishikawa et al (2010); Mishima et al (2011);Washizaki et al (2012). For an example of a coordinated hexafluorophosphate ion, see: Noro et al (2011).…”

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“…3,5-Bis(2-pyridyl)pyrazole [Hbpypz] can be used to construct of a series of mononuclear, dinuclear and polynuclear complexes as it is well-known due to the versatile properties of the ligand (Klingele et al, 2009). The Hbpypz has four N donors by deprotonation; the two N atoms in a pyrazole moiety and two N atoms in pyridine moieties.…”

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Bis[μ-3,5-bis(pyridin-2-yl)pyrazolato]bis[(hexafluorophosphato)copper(II)]

et al. 2013

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Key indicators: single-crystal X-ray study; T = 200 K; mean (C-C) = 0.003 Å; R factor = 0.027; wR factor = 0.074; data-to-parameter ratio = 14.9.The title dinuclear complex molecule, [Cu 2 (C 13 H 9 N 4 ) 2 (PF 6 ) 2 ], lies about an inversion center. The Cu II atom shows a squarepyramidal coordination geometry with the basal plane formed by four N atoms of the two bis-chelating 3,5-bis(pyridin-2-yl)pyrazolate ions and with one F atom of the hexafluorophosphate ion in the apical position. Molecules are stacked in a column along the a axis through C-HÁ Á ÁF hydrogen bonds. The columns are further linked by other C-HÁ Á ÁF hydrogen bonds, forming a three-dimensional network. Related literature

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“…[1,2] Dinuclear metal complexes have received substantial scientific interest as model systems for various metalloenzymes. The dinuclear nickel(II) [3] and zinc(II) [4] complexes of several dinucleating ligands consisting of two connected tripodal or macrocyclic entities with aromatic and aliphatic nitrogen donor functions have been studied by Meyer et al All of these ligands contain a pyrazole-based bridging unit, which coordinates in its deprotonated form with each nitrogen donor to only one metal center resulting in the proximity of the metal atoms essential for cooperative effects.…”

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confidence: 99%

Halido‐Bridged Dinuclear Nickel and Zinc Complexes with a Bis(tripodal) Octaamine Ligand – Unusual Coordination Mode of an ortho‐Phenylenediamine

2009

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A potentially dinucleating octaamine ligand H6‐4 consisting of two aliphatic tripodal tetraamine units connected by an ortho‐phenylenediamine spacer has been synthesized. Treatment of H6‐4 with Ni(BF4)2·6H2O or H10‐4(BF4)4 with Et2Zn in the presence of a halide source leads to the formation of the dinuclear complexes [Ni2(μ‐Cl)2(H6‐4)](BF4)2 (5) and [Zn(μ‐F)(H6‐4)](BF4)3 (6), respectively, which were structurally characterized by X‐ray diffraction studies. In both 5 and 6 the ligand coordinates with four nitrogen donors to each metal center. The ortho‐phenylenediamine bridging unit coordinates in an unprecedented fashion with each of its amine functions to only one of the metal centers. The dinickel complex 5 possesses two bridging chlorido ligands that differ notably in their Cl–Ni bond lengths, due to interactions of four amine N–H protons with one of the chlorido bridges leading to a reduced donor ability. The dizinc complex 6 was synthesized without addition of an external halide source. The two zinc atoms in 6 facilitate the abstraction of a fluoride from a tetrafluoroborate anion through a cooperative activation by the two adjacent metal centers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Polynuclear transition metal complexes of metal⋯metal-bridging compartmental pyrazolate ligands

Cited by 217 publications

References 176 publications

Siamese‐Twin Porphyrin: A Pyrazole‐Based Expanded Porphyrin Providing a Bimetallic Cavity

Siamese‐Twin Porphyrin: A Pyrazole‐Based Expanded Porphyrin Providing a Bimetallic Cavity

Bis[μ-3,5-bis(pyridin-2-yl)pyrazolato]bis[(hexafluorophosphato)copper(II)]

Halido‐Bridged Dinuclear Nickel and Zinc Complexes with a Bis(tripodal) Octaamine Ligand – Unusual Coordination Mode of an ortho‐Phenylenediamine

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