Oxidation Efficiencies of High Spin Fe(II)–Azo Amino Acid Complexes by Potassium Peroxydisulfate: Initial State–Transition State Solvation Effects

Rate constants are reported for hexachloroiridate(IV) oxidation of iodide in methanol–, ethanol–, t-butyl alcohol–, ethylene glycol–, glycerol–, acetone–, acetonitrile–, and dimethyl sulphoxide – water solvent mixtures, and for the hexachloroiridate(IV) oxidation of catechol in methanol–water mixtures. With the aid of ancillary solubility data and measurements, solvent effects on reactivity have been analysed into initial state and transition state components. In the latter, there are probably both electron transfer and diffusion contributions since it is not possible to identify uniquely the separate kinetic steps associated with the activation process. In these redox systems, however, transition state solvation changes dominate. This conclusion is compared with initial state – transition state effects in the reaction of catechol with hexahydroxoantimonic acid, in the bromate oxidation of bromide, the peroxodisulphate oxidation of iodide, and with patterns established earlier for substitution at inorganic centres. In view of some disagreements and uncertainties in the literature concerning the number of molecules of water of crystallisation in potassium hexachloroiridate(III) and hexachloroiridate(IV), this matter, of considerable importance to hexachloroiridate transfer parameter estimation, is briefly reviewed.

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Initial state and transition state solvation effects in the cobaltitungstate oxidation of iodide in binary aqueous solvent mixtures

Transition Metal Chemistry ◽

10.1007/bf00623798 ◽

1982 ◽

Vol 7 (1) ◽

pp. 10-13 ◽

Cited By ~ 6

Author(s):

Michael J. Blandamer ◽

John Burgess ◽

Philip P. Duce ◽

Robert I. Haines ◽

Alexander McAuley

Keyword(s):

Transition State ◽

Solvent Mixtures ◽

Initial State ◽

Solvation Effects ◽

Aqueous Solvent Mixtures ◽

Aqueous Solvent

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Potentiometric study of enantioselective effects in α-amino acid complexes of copper(II)

Inorganica Chimica Acta ◽

10.1016/s0020-1693(00)83787-1 ◽

1985 ◽

Vol 104 (1) ◽

pp. 63-67 ◽

Cited By ~ 6

Author(s):

I.L. Ulanovski ◽

A.A. Kurganov ◽

V.A. Davankov

Keyword(s):

Amino Acid ◽

Potentiometric Study ◽

Amino Acid Complexes

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Synthesis, Characterization, and Non-Covalent Interactions of Palladium(II)-Amino Acid Complexes

Molecules ◽

10.3390/molecules26144331 ◽

2021 ◽

Vol 26 (14) ◽

pp. 4331

Author(s):

David B. Hobart ◽

Michael A. G. Berg ◽

Hannah M. Rogers ◽

Joseph S. Merola

Keyword(s):

Amino Acid ◽

High Resolution Mass Spectrometry ◽

Resonance Spectroscopy ◽

Spectroscopic Techniques ◽

X Ray Diffraction ◽

Amino Acid Complexes ◽

Acetone Water ◽

Square Planar ◽

Non Covalent Interactions ◽

Covalent Interactions

The reaction of palladium(II) acetate with acyclic amino acids in acetone/water yields square planar bis-chelated palladium amino acid complexes that exhibit interesting non-covalent interactions. In all cases, complexes were examined by multiple spectroscopic techniques, especially HRMS (high resolution mass spectrometry), IR (infrared spectroscopy), and 1H NMR (nuclear magnetic resonance) spectroscopy. In some cases, suitable crystals for single crystal X-ray diffraction were able to be grown and the molecular structure was obtained. The molecular geometries of the products are discussed. Except for the alanine complex, all complexes incorporate water molecules into the extended lattice and exhibit N-H···O and/or O···(HOH)···O hydrogen bonding interactions. The non-covalent interactions are discussed in terms of the extended lattice structures exhibited by the structures.

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