Design, Preparation and Characterization of the Adducts of the Bis‐Amido Cobalticinium Complex [CoIII(η5‐C5H4CONHC5H4N)2][PF6] with Fumaric and Maleic Acids

Braga, Dario; Giaffreda, Stefano Luca; Polito, Marco; Grepioni, Fabrizia

doi:10.1002/ejic.200500143

Cited by 13 publications

(4 citation statements)

References 72 publications

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“…The calculated N···F distances are ca. 0.2 Å shorter than those observed in hydrogen-bonded adducts of cationic transition metal complexes with PF 6 - anions. , The two PF 6 - units show a pseudo-octahedral geometry with the distance between P and the fluorine atom engaged in the hydrogen bonding interaction being significantly longer than the other P−F distances (1.77 vs 1.62 Å in the average). Structures with two cis -fluorine atoms of each PF 6 - unit pointing to the cofacial pair of trans pyrrole N−H groups were also theoretically explored for {H 4 TPP(PF 6 ) 2 }.…”

Section: Resultsmentioning

confidence: 82%

Evidence for Tetraphenylporphyrin Monoacids

et al. 2007

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Upon dilution from a concentrated solution in dichloromethane, the diacid form of tetraphenylporphyrin {H(4)TPP(X)(2)} (X = Cl, PF(6) and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, TFPB) affords eventually the unprotonated free base species H(2)TPP. At a difference of chloride, in the case of PF(6)(-) and TFPB(-) anions the conversion occurs with the intermediacy of a species, which has been assigned to a monoacid derivative on the basis of UV/vis absorption, fluorescence emission (static and dynamic), and resonance light scattering. Ground-state gas-phase geometries have been calculated both for the diacid {H(4)TPP(PF(6))(2)} and monoacid {H(4)TPP(PF(6))(2)} and {H(3)TPP(Cl)} species at the DFT/BP86 level of theory. TDDFT calculations using different functionals (BP86, SAOP, and B3LYP) have been exploited to provide electronic vertical excitation energies and oscillator strengths, yielding a remarkably good description of the optical spectra for these compounds and supporting the identification of the monoacid species. Gas-phase thermodynamic calculations on the chloride species provide an estimate of the Gibbs free energy changes associated with the two protonation steps, supporting the observed different behavior of this anion with respect to PF(6)(-) and TFPB(-).

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Section: Resultsmentioning

confidence: 82%

Evidence for Tetraphenylporphyrin Monoacids

et al. 2007

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“…Alternatively, the reactions could be conducted in neat amine. In this case the reactions were complete at 35…”

Section: Account Syn Lettmentioning

confidence: 99%

Metallocenium Chemistry and Its Emerging Impact on Synthetic Macromolecular Chemistry

Yan

Pageni

Kabir

et al. 2016

Synlett

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Cationic metallocenes (or metalloceniums) are a class of sandwich-type compounds with cationic metal centers, which are usually iron, cobalt, or rhodium. These unique charged complexes have received wide attention owing to both rich electrochemistry and the positive charge associated with the transition metal. They are potential building blocks for fabricating functional polyelectrolytes and for possible biomedical applications. As the basis of all metallocenium-containing materials, the synthetic chemistry of metallocenium has been a recently emerging field. In this account, we give a brief summary of metallocenium chemistry. Furthermore, its emerging impact on functional macromolecules is also covered. 1 Introduction 2 Cobaltocenium-Containing Derivatives and Macromolecules 2.1 General Synthetic Routes 2.2 Disubstituted Cobaltoceniums 2.3 Carboxycobaltocenium and Its Derivatives 2.4 Ethynylcobaltocenium and Its Derivatives 2.5 Other Cobaltocenium Derivatives 3 Rhodocenium-Containing Derivatives and Macromolecules 4 Summary and Outlook

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“…[15][16][17] Hydrazones (where R = H) can form supramo-lecular arrays in the solid state due to the presence of the protic NH 2 group available for hydrogen bonding, a feature which is being exploited in the crystal engineering field. [18][19][20][21][22][23] The ligands chosen for this study are shown in Figure 2, with the expectation of conveying different steric demands on the titanium(IV) centre and facilitating the formation of different arrays in the solid state. …”

Section: Introductionmentioning

confidence: 99%

Titanium(IV) Complexes of Hydrazones and Azines

et al. 2006

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The coordination modes of various azines (C=N-N=C) and hydrazones (C=N-NR 2 ) with titanium(IV) are investigated. Five ligands were studied, two hydrazones 1H-2H and three azines 3H 2 -5H 2 , and it was found that hydrazones form monomers and azines form dimers in the solid state. The hydrogen-bonded arrays observed for the hydrazones were significantly different for the two ligands, with one forming a

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Design, Preparation and Characterization of the Adducts of the Bis‐Amido Cobalticinium Complex [Co^III(η⁵‐C₅H₄CONHC₅H₄N)₂][PF₆] with Fumaric and Maleic Acids

Cited by 13 publications

References 72 publications

Evidence for Tetraphenylporphyrin Monoacids

Evidence for Tetraphenylporphyrin Monoacids

Metallocenium Chemistry and Its Emerging Impact on Synthetic Macromolecular Chemistry

Titanium(IV) Complexes of Hydrazones and Azines

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