Doubly pyridazine-bridged macrocyclic complexes of copper in +1, +2 and mixed valent oxidation states

Brooker, Sally; Davidson, Tony C.; Hay, Sarah J.; Kelly, Robert J.; Kennepohl, Dietmar; Plieger, Paul G.; Moubaraki, Boujemaa; Murray, Keith S.; Bill, Eckhard; Bothe, Eberhard

doi:10.1016/s0010-8545(00)00399-4

Cited by 63 publications

(60 citation statements)

References 7 publications

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“…The above crystals were characterised by X-ray crystallography (see later). [4,13] is observed ( Figure 1). Complex 1 ¥ CH 3 CN crystallised as orange needles in which a side-by-side architecture is observed ( Figure 2 4 , resulted in that instance, although it should be noted that on occasions the samples were brown due to the spontaneous formation of traces of highly coloured copper(i) contaminants.…”

Section: Resultsmentioning

confidence: 93%

“…The key difference between the reactions of copper(ii) with the acyclic ligand L2 and macrocyclic ligand L1 is that in the former a tetrahedral arrangement of the donor atoms, suitable for stabilising copper(i), is readily achievable, whereas this is not the case for the L1 macrocycle; therefore the squarepyramidal copper(ii) complex can be isolated when a copper(ii) starting material is employed in the transmetallation reaction. [9,13] In the case of the iron(ii) complexes, the reaction of one equivalent of ligand L2 with one equivalent of iron chloride (no precautions were taken to ensure that this reagent was exclusively iron(ii) chloride) gave complex [ ). As expected, the infrared spectra of the complexes 1 ± 9 have many similar features.…”

Section: Resultsmentioning

confidence: 99%

“…The magnetic susceptibilities were measured by using a Quantum Design MPMS 5 Squid magnetometer as described previously. [13,14] The Mˆssbauer spectrum was obtained using a conventional constant acceleration drive with a symmetrical sawtooth waveform. The source of 57 Co in rhodium was maintained at room temperature.…”

Section: Resultsmentioning

confidence: 99%

“…All other measurements were carried out as described previously. [7,13] . The resulting orange-yellow mixture was stirred at room temperature for 6 h, during which time 9 precipitated as an orange powder.…”

Section: Resultsmentioning

confidence: 99%

“…Either way these compounds are clearly stable in solution so their formation is not dependent on crystallisation effects. Because of the low solubility of complex 3, even in DMF, quaternary carbons cannot be seen in the 13 C NMR spectrum, due to their long relaxation times.…”

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confidence: 99%

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Coordination Algorithms Control Molecular Architecture: [Cu^I₄(L2)₄]⁴⁺ Grid Complex Versus [M^II₂(L2)₂X₄]^y+ Side‐By‐Side Complexes (M=Mn, Co, Ni, Zn; X=Solvent or Anion) and [Fe^II(L2)₃][Cl₃Fe^IIIOFe^IIICl₃]

Lan

Kennepohl

Moubaraki

et al. 2003

Chemistry A European J

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The synthesis and characterisation of a pyridazine-containing two-armed grid ligand L2 (prepared from one equivalent of 3,6-diformylpyridazine and two equivalents of p-anisidine) and the resulting transition metal (Zn, Cu, Ni, Co, Fe, Mn) complexes (1-9) are reported. Single-crystal X-ray structure determinations revealed that the copper(I) complex had self-assembled as a [2 x 2] grid, [Cu(I) (4)(L2)(4)][PF(6)](4).(CH(3)CN)(H(2)O)(CH(3)CH(2)OCH(2)CH(3))(0.25) (2.(CH(3)CN)(H(2)O)(CH(3)CH(2)OCH(2)CH(3))(0.25)), whereas the [Zn(2)(L2)(2)(CH(3)CN)(2)(H(2)O)(2)][ClO(4)](4).CH(3)CN (1.CH(3)CN), [Ni(II) (2)(L2)(2)(CH(3)CN)(4)][BF(4)](4).(CH(3)CH(2)OCH(2)CH(3))(0.25) (5 a.(CH(3)CH(2)OCH(2)CH(3))(0.25)) and [Co(II) (2)(L2)(2)(H(2)O)(2)(CH(3)CN)(2)][ClO(4)](4).(H(2)O)(CH(3)CN)(0.5) (6 a.(H(2)O)(CH(3)CN)(0.5)) complexes adopt a side-by-side architecture; iron(II) forms a monometallic cation binding three L2 ligands, [Fe(II)(L2)(3)][Fe(III)Cl(3)OCl(3)Fe(III)].CH(3)CN (7.CH(3)CN). A more soluble salt of the cation of 7, the diamagnetic complex [Fe(II)(L2)(3)][BF(4)](2).2 H(2)O (8), was prepared, as well as two derivatives of 2, [Cu(I) (2)(L2)(2)(NCS)(2)].H(2)O (3) and [Cu(I) (2)(L2)(NCS)(2)] (4). The manganese complex, [Mn(II) (2)(L2)(2)Cl(4)].3 H(2)O (9), was not structurally characterised, but is proposed to adopt a side-by-side architecture. Variable temperature magnetic susceptibility studies yielded small negative J values for the side-by-side complexes: J=-21.6 cm(-1) and g=2.17 for S=1 dinickel(II) complex [Ni(II) (2)(L2)(2)(H(2)O)(4)][BF(4)](4) (5 b) (fraction monomer 0.02); J=-7.6 cm(-1) and g=2.44 for S= 3/2 dicobalt(II) complex [Co(II) (2)(L2)(2)(H(2)O)(4)][ClO(4)](4) (6 b) (fraction monomer 0.02); J=-3.2 cm(-1) and g=1.95 for S= 5/2 dimanganese(II) complex 9 (fraction monomer 0.02). The double salt, mixed valent iron complex 7.H(2)O gave J=-75 cm(-1) and g=1.81 for the S= 5/2 diiron(III) anion (fraction monomer=0.025). These parameters are lower than normal for Fe(III)OFe(III) species because of fitting of superimposed monomer and dimer susceptibilities arising from trace impurities. The iron(II) centre in 7.H(2)O is low spin and hence diamagnetic, a fact confirmed by the preparation and characterisation of the simple diamagnetic iron(II) complex 8. Mössbauer measurements at 77 K confirmed that there are two iron sites in 7.H(2)O, a low-spin iron(II) site and a high-spin diiron(III) site. A full electrochemical investigation was undertaken for complexes 1, 2, 5 b, 6 b and 8 and this showed that multiple redox processes are a feature of all of them.

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Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

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Coordination Algorithms Control Molecular Architecture: [Cu^I₄(L2)₄]⁴⁺ Grid Complex Versus [M^II₂(L2)₂X₄]^y+ Side‐By‐Side Complexes (M=Mn, Co, Ni, Zn; X=Solvent or Anion) and [Fe^II(L2)₃][Cl₃Fe^IIIOFe^IIICl₃]

Lan

Kennepohl

Moubaraki

et al. 2003

Chemistry A European J

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Synthetic Methods for Macrocyclic Polyamines

2017

Macrocyclic Polyamines

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Jellyfish‐type Dinuclear Hafnium Azido Complexes: Synthesis and Reactivity

Lin,

Cui,

Xie

et al. 2023

Chemistry An Asian Journal

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Di‐ and multinuclear hafnium complexes bridged by ligands have been rarely reported. In this article, a novel 3,5‐disubstituted pyrazolate‐bridged ligand LH5 with two [N2N]2−‐type chelating side arms was designed and synthesized, which supported a series of dinuclear hafnium complexes. Dinuclear hafnium azides [LHf2(μ‐1,1‐N3)2(N3)2][Na(THF)4] 3 and [LHf2(μ‐1,1‐N3)2(N3)2][Na(2,2,2‐Kryptofix)] 4 were further synthesized and structurally characterized, featuring two sets of terminal and bridging azido ligands like jellyfishes. The reactivity of 3 under reduction conditions was conducted, leading to a formation of a tetranuclear hafnium imido complex [L1Hf2(μ1‐NH)(N3){μ2‐K}]2 5. DFT calculations revealed that the mixed imido azide 5 was generated via an intramolecular C−H insertion from a putative dinuclear HfIV‐nitridyl intermediate.

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Doubly pyridazine-bridged macrocyclic complexes of copper in +1, +2 and mixed valent oxidation states

Cited by 63 publications

References 7 publications

Coordination Algorithms Control Molecular Architecture: [Cu^I₄(L2)₄]⁴⁺ Grid Complex Versus [M^II₂(L2)₂X₄]^y+ Side‐By‐Side Complexes (M=Mn, Co, Ni, Zn; X=Solvent or Anion) and [Fe^II(L2)₃][Cl₃Fe^IIIOFe^IIICl₃]

Coordination Algorithms Control Molecular Architecture: [Cu^I₄(L2)₄]⁴⁺ Grid Complex Versus [M^II₂(L2)₂X₄]^y+ Side‐By‐Side Complexes (M=Mn, Co, Ni, Zn; X=Solvent or Anion) and [Fe^II(L2)₃][Cl₃Fe^IIIOFe^IIICl₃]

Synthetic Methods for Macrocyclic Polyamines

Jellyfish‐type Dinuclear Hafnium Azido Complexes: Synthesis and Reactivity

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Doubly pyridazine-bridged macrocyclic complexes of copper in +1, +2 and mixed valent oxidation states

Cited by 63 publications

References 7 publications

Coordination Algorithms Control Molecular Architecture: [CuI4(L2)4]4+ Grid Complex Versus [MII2(L2)2X4]y+ Side‐By‐Side Complexes (M=Mn, Co, Ni, Zn; X=Solvent or Anion) and [FeII(L2)3][Cl3FeIIIOFeIIICl3]

Coordination Algorithms Control Molecular Architecture: [CuI4(L2)4]4+ Grid Complex Versus [MII2(L2)2X4]y+ Side‐By‐Side Complexes (M=Mn, Co, Ni, Zn; X=Solvent or Anion) and [FeII(L2)3][Cl3FeIIIOFeIIICl3]

Synthetic Methods for Macrocyclic Polyamines

Jellyfish‐type Dinuclear Hafnium Azido Complexes: Synthesis and Reactivity

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Product

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Coordination Algorithms Control Molecular Architecture: [Cu^I₄(L2)₄]⁴⁺ Grid Complex Versus [M^II₂(L2)₂X₄]^y+ Side‐By‐Side Complexes (M=Mn, Co, Ni, Zn; X=Solvent or Anion) and [Fe^II(L2)₃][Cl₃Fe^IIIOFe^IIICl₃]

Coordination Algorithms Control Molecular Architecture: [Cu^I₄(L2)₄]⁴⁺ Grid Complex Versus [M^II₂(L2)₂X₄]^y+ Side‐By‐Side Complexes (M=Mn, Co, Ni, Zn; X=Solvent or Anion) and [Fe^II(L2)₃][Cl₃Fe^IIIOFe^IIICl₃]