Multielectron oxidation in a ferromagnetically coupled dinickel(<scp>ii</scp>) triple mesocate

Ferrando-Soria, Jesús; Fabelo, Óscar; Castellano, Marı́a; Cano, Joan; Fordham, Stephen; Zhou, Hong‐Cai

doi:10.1039/c5cc03544a

Cited by 33 publications

(20 citation statements)

References 15 publications

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“…The first oxidation event was assigned to the 1e À oxidation of 1 (Ni II 2 )t oaputative mixedvalent Ni II Ni III species( defined as 2), followed by as ubsequent 1e À oxidation to ap utative high valent Ni III 2 species( defined as 3). Zhou and co-workers [23] observeds imilar multiple 1e À oxidations of at riple meso-helicate Ni 2 complex from Ni II 2 !Ni II Ni III !Ni III 2 and, at higherp otential, from Ni III 2 ! Ni III Ni IV !Ni IV 2 .F or bis-m-hydroxo-Ni II 2 complexes, Itoh andc oworkers [12b] reportedn os tepwise oxidation in cyclic voltammetry experiments,o bserving only as ingle 1e À oxidation from Ni II 2 to Ni II Ni III ,p resumably due to the instability of the high valent bis-m-oxo-Ni III 2 state, which required low temperature (À90 8C) to be observed.…”

Section: Synthesis and Characterisation Of [(Ni II (Oh)(l)) 2 ] 2à à (1)mentioning

confidence: 99%

Preparation and Characterisation of a Bis‐μ‐Hydroxo‐Ni^III₂ Complex

Spedalotto

Gericke

Lovisari

et al. 2019

Chemistry A European J

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Hydroxide‐bridged high‐valent oxidants have been implicated as the active oxidants in methane monooxygenases and other oxidases that employ bimetallic clusters in their active site. To understand the properties of such species, bis‐μ‐hydroxo‐NiII2 complex (1) supported by a new dicarboxamidate ligand (N,N′‐bis(2,6‐dimethyl‐phenyl)‐2,2‐dimethylmalonamide) was prepared. Complex 1 contained a diamond core made up of two NiII ions and two bridging hydroxide ligands. Titration of the 1 e− oxidant (NH4)2[CeIV(NO3)6] with 1 at −45 °C showed the formation of the high‐valent species 2 and 3, containing NiIINiIII and NiIII2 diamond cores, respectively, maintaining the bis‐μ‐hydroxide core. Both complexes were characterised using electron paramagnetic resonance, X‐ray absorption, and electronic absorption spectroscopies. Density functional theory computations supported the spectroscopic assignments. Oxidation reactivity studies showed that bis‐μ‐hydroxide‐NiIII2 3 was capable of oxidizing substrates at −45 °C at rates greater than that of the most reactive bis‐μ‐oxo‐NiIII complexes reported to date.

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Section: Synthesis and Characterisation Of [(Ni II (Oh)(l)) 2 ] 2à à (1)mentioning

confidence: 99%

Preparation and Characterisation of a Bis‐μ‐Hydroxo‐Ni^III₂ Complex

Spedalotto

Gericke

Lovisari

et al. 2019

Chemistry A European J

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“…IR (KBr pellet, cm -1 ): 3295 ν (N-H), 3060 ν (C-H), 1682 ν (C=O); 1608 ν (C=C); 1544 ν (N-C). 1 H-NMR (d 6 -DMSO, ppm): 10.72 (s, 2H), 9.28 (s, 2H), 8.92 (d, 2H), 8.80 (d, 2H), 8.55 (s, 1H), 7.59 (d, 2H), 7.34 (t, 1H).…”

Section: Synthesis Of 13-bis(pyrimidine-2-carboxamide)benzene (H2bpcmentioning

confidence: 99%

“…To a solution of 1 (0.1g, 0.081 mmol) in a mixture of water/acetonitrile 1/1 [Co(H2O)5Ni2(bpcb)3]•15H2O (6) This complex was obtained following the same synthetic procedure described above for complex 5 but using Co(ClO4)2•6H2O (0.090 g, 0.24 mmol) as the metallic salt added to 1. Yield: 38 %.…”

Section: [Ni(h2o)5ni2(bpcb)3]•18h2o (5)mentioning

confidence: 99%

“…If the Ni2 units are considered as spacers and the Mn 3+ ions as nodes, this connectivity gives rise to a (6,3) honeycomb corrugated layered structure extended in the ab plane ( Figure 5). Each hexagonal ring is formed by six [Ni2(bpcb)3] 2dinuclear units and six [Mn(acen)] + cations, which alternate, so that the former occupy the vertices and the latter are located on the edges of the hexagon (Figures 5 and S4).…”

Section: Crystal Structuresmentioning

confidence: 99%

“…As expected, this complex exhibits a ferromagnetic interaction between the metal ions, and interesting multi-electron oxidation processes. 6 Scheme 2: Structure of the ligands H2mbpb, H2bcpb, H2bpzpb and their potential coordination sites.…”

Section: Introductionmentioning

confidence: 99%

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Synthetic ability of dinuclear mesocates containing 1,3-bis(diazinecarboxamide)benzene bridging ligands to form complexes of increased nuclearity. Crystal structures, magnetic properties and theoretical studies

et al. 2017

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Triple stranded Ni-metallacyclic complexes Na[Ni(bpcb)]·0.5OH·18.5HO (1) and Na[Ni(bpzcb)]·16HO (2), and double stranded Cu-metallacyclic complexes [Cu(bpcb)(HO)]·8HO (3) and [Cu(bpzcb)(HO)]·4HO (4) have been assembled from the tailored bisbidentate bridging ligands, 1,3-bis(pyrimidine-2-carboxamide)benzene (Hbpcb) and 1,3-bis(pyrazine-2-carboxamide)benzene (Hbpzcb), and the corresponding nitrate salts of the metal ions. Following the "complex as ligand" strategy, 1 can be assembled with either Ni, Co ions or the [Mn(acen)Cl] complex to afford unique, neutral, bent trinuclear molecules [MNi(bpcb)]·xHO (5 and 6) and the 2D honeycomb-like complex (PPh){[Ni(bpcb)][Mn(acen)]} (7), respectively. In these cases, the Ni units are linked to the corresponding metal ions through amidate oxygen atoms and the outward nitrogen atom of one of the pyrimidine rings of the bcpb ligand. The assembly of 2 with Ln ions (Ln = Tb, Gd) leads to one dimensional complexes of formula [{[Ni(bpzcb)]Tb(HO)}(CFSO)·THF·5HO] (8) and [{[Ni(bpzcb)]Ln(HO)(NO)}·2THF·nHO] (9 and 10) (Ln = Gd and Tb), where the dinuclear Ni units are joined to two Ln ions exclusively through amidate oxygen atoms of two different ligands. The analyses of the magnetic data indicate that 1-4 exhibit intradinuclear ferromagnetic interactions between the metal ions through a spin polarisation mechanism, as supported by DFT calculations. Trinuclear complexes 5 and 6 show predominant antiferromagnetic coupling, which is a result of an antiferromagnetic interaction between one of the Ni ions of the Ni unit and the M ion through the pyrimidine bridging fragment that is stronger than the polarised ferromagnetic interaction between the Ni ions through the bpcb ligand in the dinuclear [Ni(bpcb)] moiety. Complex 7 shows a dominant antiferromagnetic interaction between the Ni and Mn, whereas the NiLn (Ln = Gd, Tb) chain complexes present ferromagnetic interactions inside the Ni mesocate unit as well as between the Ni ions of the Ni unit and the Ln ions. The magnetic exchange interactions in these new materials have been experimentally analysed and supported by theoretical DFT studies.

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A Case Study of Mechanical Strain in Supramolecular Complexes to Manipulate the Spin State of Iron(II) Centres

et al. 2015

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Two novel supramolecular meso-helicates have been synthesized and characterized by single-crystal X-ray diffraction, variable-temperature magnetic susceptibility measurements, NMR and UV/Vis spectroscopy, mass spectrometry and density functional theory (DFT) simulations. Both compounds show a considerably high stabilization of the high-spin state of the metal centres compared with other compounds with similar types of ligands. Whereas the pyridyl complex [Fe 2 L 2 3 ] [L 2 = N,NЈ-bis(pyridin-2-ylmethylene)benzene-1,3diamine] exhibits the beginning of a spin transition at around 350 K, the imidazolyl complex [Fe 2 L 1 3 ] [L 1 = N,NЈ-bis(1H-[a] Kekulé-

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Multielectron oxidation in a ferromagnetically coupled dinickel(ii) triple mesocate

Cited by 33 publications

References 15 publications

Preparation and Characterisation of a Bis‐μ‐Hydroxo‐Ni^III₂ Complex

Preparation and Characterisation of a Bis‐μ‐Hydroxo‐Ni^III₂ Complex

Synthetic ability of dinuclear mesocates containing 1,3-bis(diazinecarboxamide)benzene bridging ligands to form complexes of increased nuclearity. Crystal structures, magnetic properties and theoretical studies

A Case Study of Mechanical Strain in Supramolecular Complexes to Manipulate the Spin State of Iron(II) Centres

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Multielectron oxidation in a ferromagnetically coupled dinickel(ii) triple mesocate

Cited by 33 publications

References 15 publications

Preparation and Characterisation of a Bis‐μ‐Hydroxo‐NiIII2 Complex

Preparation and Characterisation of a Bis‐μ‐Hydroxo‐NiIII2 Complex

Synthetic ability of dinuclear mesocates containing 1,3-bis(diazinecarboxamide)benzene bridging ligands to form complexes of increased nuclearity. Crystal structures, magnetic properties and theoretical studies

A Case Study of Mechanical Strain in Supramolecular Complexes to Manipulate the Spin State of Iron(II) Centres

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About

Preparation and Characterisation of a Bis‐μ‐Hydroxo‐Ni^III₂ Complex

Preparation and Characterisation of a Bis‐μ‐Hydroxo‐Ni^III₂ Complex