A Magnetic Resonance Study of Complex Formation between the Neutral Phenalenyl Radical and Alkali Metal Ions in Dilute Alcohol Solutions

Dwyer, David W.; Ciraolo, Michael F.; Gilbert, D.C.; Doetschman, David C.

doi:10.1021/jp0009857

Cited by 4 publications

References 18 publications

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Factors affecting the sensitivity to acid inhibition in novel acrylates characterized by secondary functionalities

Kilambi

Konopka

Stansbury

et al. 2007

J. Polym. Sci. A Polym. Chem.

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Here we demonstrate that acrylates exhibit significant rate reductions in the presence of small concentrations of protic acids (0.1–0.5 wt %) compared with the bulk monomer concentration. Dramatically different sensitivities to acid inhibition, differing by up to 2 orders of magnitude, are exhibited for various acrylates. This study examines the various factors that cause enhanced sensitivity toward acid inhibition in novel acrylates characterized by carbamate and cyclic carbonate secondary functionalities. Acid inhibition studies conducted in the presence of a highly polar solvent, such as propylene carbonate, have been performed to determine the impact of overall medium polarity and the extent of acid dissociation on the sensitivity to acid inhibition. The studies depict only a twofold increase in the parameters associated with acid inhibition, upon the addition of 70 wt % propylene carbonate, in comparison with an increase of 2 orders of magnitude for the novel acrylates. These studies indicate that the susceptibility to acid inhibition is primarily determined by the stability of the hypothesized radical–acid complex as well as its propensity to terminate with other species in the system and not by the extent of acid dissociation in the system. Furthermore, it is implied that the stability of the radical–acid complex and its propensity to terminate with other species in the system are dominated by intramolecular interactions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1287–1295, 2007

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Factors affecting the sensitivity to acid inhibition in novel acrylates characterized by secondary functionalities

Kilambi

Konopka

Stansbury

et al. 2007

J. Polym. Sci. A Polym. Chem.

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5.11 References for 5

Neugebauer¹

Landolt-Börnstein - Group II Molecules and Radicals

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Bidirectional non-innocence of the β-diketonato ligand 9-oxidophenalenone (L−) in [Ru([9]aneS3)(L)(dmso)]n, [9]aneS3 = 1,4,7-trithiacyclononane

et al. 2014

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The new compound [Ru(II)([9]aneS3)(L)(dmso)]ClO4 ([]ClO4) ([9]aneS3 = 1,4,7-trithiacyclononane, HL = 9-hydroxyphenalenone, dmso = dimethylsulfoxide) has been structurally characterised to reveal almost equal C-O bond distances of coordinated L(-), suggesting a delocalised bonding situation of the β-diketonato ligand. The dmso ligand is coordinated via the sulfur atom in the native (1+) and reduced states (1 and 1-) as has been revealed by X-ray crystallography and by DFT calculations. Cyclic voltammetry of 1+ exhibits two close-lying one-electron oxidation waves at 0.77 V and 0.94 V, and two similarly close one-electron reduction processes at -1.43 V and -1.56 V versus SCE in CH2Cl2. The electronic structures of 1n in the accessible redox states have been analysed via experiments (EPR and UV-vis-NIR spectroelectrochemistry) and by DFT/TD-DFT calculations, revealing the potential for bidirectional non-innocent behaviour of coordinated L(˙/-/˙2-). Specifically, the studies establish significant involvement of L based frontier orbitals in both the oxidation and reduction processes: [([9]aneS3)(dmso)Ru(III)-L˙](3+) (1(3+)) ⇌ [([9]aneS3)(dmso)Ru(III)-L(-)](2+)/[([9]aneS3)(dmso)Ru(II)-L˙](2+) (1(2+)) ⇌ [([9]aneS3)(dmso)Ru(II)-L(-)](+) (1(+)) ⇌ [([9]aneS3)(dmso)Ru(II)-L(˙2-)] (1) ⇌ [([9]aneS3)(dmso)Ru(II)-L(3-)](-)/[([9]aneS3)(dmso)Ru(I)-L(˙2-)](-) (1-).

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A Magnetic Resonance Study of Complex Formation between the Neutral Phenalenyl Radical and Alkali Metal Ions in Dilute Alcohol Solutions

Cited by 4 publications

References 18 publications

Factors affecting the sensitivity to acid inhibition in novel acrylates characterized by secondary functionalities

Factors affecting the sensitivity to acid inhibition in novel acrylates characterized by secondary functionalities

5.11 References for 5

Bidirectional non-innocence of the β-diketonato ligand 9-oxidophenalenone (L−) in [Ru([9]aneS3)(L)(dmso)]n, [9]aneS3 = 1,4,7-trithiacyclononane

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