Mixed-valence properties of ligand-bridged iron-cyano complexes

Felix, F. W.; Lüdi, A.

doi:10.1021/ic50185a015

Cited by 63 publications

(36 citation statements)

References 2 publications

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“…The absorption maxima (t2, + LT* metal-to-ligand charge transfer (MLCT) band) and molar absorptivity coefficients (Table 1) for a number of the complexes in this study have been reported previously (9,12,19,20). The shift in A , , ,…”

Section: Resultssupporting

confidence: 61%

Ligand substitution reactions of pentacyanoferrate(II) complexes with N-heterocyclic cations in aqueous solution

Macartney¹,

Warrack²

1989

Can. J. Chem.

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This paper is dedicated to Professor Ronald J. Gillespie on the occasion of his 65th birthday DONAL HUGH MACARTNEY and LAUREN JEAN WARRACK. Can. J. Chem. 67, 1774 (1989). Kinetic and spectroscopic studies have been carried out in aqueous solution on the formation (from F~( c N )~O H~' -) and dissociation of pentacyanoferrate(I1) complexes containing 1-(4-pyridy1)pyridinium and the neutral, protonated, and N-methylated forms of 4,4'-bipyridine (BPY), 1,2-bis(4-pyridy1)ethane (BPA), and trans-l,2-bis(4-pyridy1)ethylene (BPE). The pH dependences of the formation kinetics have been analyzed in terms of the specific rate and acid dissociation constants for these ligands. The rate constants (25.0°C, I = 0.10 M) for the formation of the dinuclear complexes ( N C )~F~L F~( C N )~~-have been determined for BPY (50 M-' s-I), BPA (66 M-' s-), BPE (95 M-' s-I), and pyrazine (10 M-I S-I), and are compared with the respective rate constants for the formation of (NC)5FeLCo(NH3)5. The relationships between the formation rate constants and the size of the ligand, the number of donor sites, and the magnitude and position of charges on the ligand are discussed in terms of an ion-pair dissociative mechanism.

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Section: Resultssupporting

confidence: 61%

Ligand substitution reactions of pentacyanoferrate(II) complexes with N-heterocyclic cations in aqueous solution

Macartney¹,

Warrack²

1989

Can. J. Chem.

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“…Description of route 2 for 11: An aqueous solution of K 6 [Fe 2 (mbpy)(CN) 10 ] [30] (0.15 g, 0.20 mmol) in H 2 O (10 mL) was frozen under liquid N 2 , powdered, and placed into a cylindric Dewar container as the lowest layer. Pure, granulated ice (from ca.…”

Section: Preparation Of 8 ± 12mentioning

confidence: 99%

Spontaneously Organizing Metal Connectors as Supramolecular Structure Directors of Two‐ and Three‐Dimensional Organometallic Assemblies

Eckhardt

Hanika-Heidl

Fischer

2003

Chemistry A European J

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The supramolecular interplay of Me(3)Sn(+) and [M(CN)(2n)](n-) ions (n=3 and 4) with either 4,4'-bipyridine (bpy), trans-bis(4-pyridyl)ethene (bpe) or 4cyanopyridine (cpy) in the presence of H(2)O has been investigated for the first time. Crystal structures of the six novel assemblies: [(Me(3)Sn)(4)Mo(IV)(CN)(8).2 H(2)O.bpy] (8) and [(Me(3)Sn)(4)Mo(IV)(CN)(8).2 H(2)O.bpe] (8 a; isostructural), [(Me(3)Sn)(3)Fe(III)(CN)(6).4 H(2)O.bpy] (9), [(Me(3)Sn)(3)Co(III)(CN)(6).3 H(2)O.3/2 bpy] (10), [(Me(3)Sn)(4)Fe(II)(CN)(6).H(2)O.3/2 bpy] (11), and [(Me(3)Sn)(4)Ru(II)(CN)(6).2 H(2)O.3/2 cpy] (12) are presented. H(2)O molecules are usually coordinated to tin atoms and involved in two significant O-H.N hydrogen bonds, wherein the nitrogen atoms belong either to bpy (bpe, cpy) molecules or to M-coordinated cyanide ligands. Extended supramolecular assemblies such as -CN-->Sn(Me(3))<--O(H.)H.N(L)N.HO(H.)-->Sn(Me(3))<--NC- (L=bpy, bpe or cpy) function as efficient metal connectors (or spacers) in the structures of all six compounds. Only in the three-dimensional framework of 11, one third of all bpy molecules is involved in coordinative N-->Sn bonds. The supramolecular architecture of 9 involves virtually non-anchored (to cyanide N atoms), Me(3)Sn(+) units with a strictly planar SnC(3) skeleton, and two zeolitic H(2)O molecules. Pyrazine (pyz) is surprisingly reluctant to afford assemblies similar to 8-12, however, the genuine host-guest systems [(Me(3)Sn)(4)Mo(CN)(8).0.5pyz] and [(Me(3)Sn)(4)Mo(CN)(8).pym] (pym=pyrimidine) could be isolated and also structurally characterized.

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“…In these works, it has been proved that some electrochemical properties are dependent on the rate of electrogeneration, obtaining narrower and sharper voltammetric peaks for the higher current deposited PB films. These PB films were galvanostatically generated from FeCl 3 and K 3 Fe(CN) 6 The crystal structure of these i-PB films has been reported to be cubic face centered [15][16][17][18][19][20][21][22] with space group symmetry Fm3m. i-PB films present structural vacancies, 1/4 of the ferrocyanide sites.…”

Section: Introductionmentioning

confidence: 99%

Identification of electroactive sites in Prussian Yellow films

Agrisuelas

Garcı́a-Jareño

Moreno-Guerrero

et al. 2013

Electrochimica Acta

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Abstract.Prussian Blue films were electrogenerated on the surface of the transparent ITO electrodes. The electrochemical oxidation to the Prussian Yellow form was investigated by means of in situ voltammetry and Vis-NIR spectroscopic techniques. Changes of the whole spectra between 400 and 950 nm were analyzed and three characteristic wavelengths were selected to in situ follow the electrochemical changes of the films.Voltammetric peaks and absorbance derivative curves at these three wavelengths were deconvoluted and were interpreted such as the overlapping of different electrochemical processes. The correlation between these overlapped processes has allowed proposing three different electrochemical processes for the interpretation of the whole electrochemical response. One of these processes corresponds to the oxidation of

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Mixed-valence properties of ligand-bridged iron-cyano complexes

Cited by 63 publications

References 2 publications

Ligand substitution reactions of pentacyanoferrate(II) complexes with N-heterocyclic cations in aqueous solution

Ligand substitution reactions of pentacyanoferrate(II) complexes with N-heterocyclic cations in aqueous solution

Spontaneously Organizing Metal Connectors as Supramolecular Structure Directors of Two‐ and Three‐Dimensional Organometallic Assemblies

Identification of electroactive sites in Prussian Yellow films

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