Topic
Aquation
About: Aquation is a research topic. Over the lifetime, 1443 publications have been published within this topic receiving 17507 citations.
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TL;DR: In this paper, the solvent and β-deuterium isotope effects for Co(tren)Cl2+ have been studied in H2O and D2O at 25°.
3 citations
TL;DR: In this article, the kinetics of base hydrolysis of (αβS) (salicylato) (tetraethylenepentamine) cobalt(III) have been investigated in aquo-organic solvent media at 15.0 < t, °C < 40.0, and I = 0.
Abstract: The kinetics of base hydrolysis of (αβS) (salicylato) (tetraethylenepentamine) cobalt(III) have been investigated in aquo-organic solvent media at 15.0 < t, °C < 40.0, and I = 0.10 mol dm (ClO4−) using propane-2-ol (⩽70% v/v), t-butanol (⩽60% v/v), acetone (⩽70% v/v), acetonitrile (⩽50% v/v), and ethylene glycol (⩽70% v/v) as cosolvents. Both the spontaneous and base-catalyzed hydrolysis of the phenoxide species [(tetren)CoO2CC6H4O]+ were appreciably accelerated by the cosolvents PriOH, ButOH, Me2CO, and MeCN. On the contrary the base hydroylsis (k2) was retarded while spontaneous aquation (k1) was accelerated to a small extent with increased EG content. Variation of log k1 and log k (k = k2 at I = 0) with mole fraction (X0.S) or reciprocal of the relative permitivity (Ds−1) of the media were nonlinear. The transfer free energy of the transition state relative to that of the initial state of the substrate for transfer of species from water to mixed solvents also varied nonlinearly with X0.S, or Ds−1 indicating solvent specificity. The activation parameters, ΔH≠ and ΔS≠ varied nonlinearly with solvent composition exhibiting extrema. The preferential solvation and solvent structural effects mediated the kinetics and energetics of the reaction. © 1995 John Wiley & Sons, Inc.
3 citations
3 citations
01 Jan 1987
TL;DR: Cameron and Bocarsly as mentioned in this paper showed that up to four electrons can be transferred in this pro- cess leading to the formation of platinum metal and aldehydes or ketones depending on whether a primary or secondary alcohol is initially employed.
Abstract: Although the photochemistry of octahedral haloplatinum (IV) complexes has been extensively investigated, it has always been viewed in terms of ligand substi- tution processes. However, the preference of platinum for the (II) and (IV) oxidation states, and the previous observation (Cox et al., 1972) that photo- aquation of [PtCl6]2- can involve a Pt(III) intermediate suggests that such complexes may be capable of photoinduced multielectron charge transfer. Such a capability has now been demonstrated in the photoinitiated reaction of [PtCl6]2- with alcohols. Up to four electrons can be transferred in this pro- cess leading to the formation of platinum metal (Cameron and Bocarsly, 1986) and aldehydes or ketones depending on whether a primary or secondary alcohol is initially employed. Of special interest is the finding that primary alcohols are not overoxidized to the acid. Further aldehyde formation can be carried out catalytically by addition of O2/CuCl2 to the reaction mixture as a reoxidant of lower platinum oxidation states back to Pt(IV) (Cameron and Bocarsly, 1985).
3 citations
TL;DR: A binding mechanism is postulated for the inhibition of the dehydrogenases by direct displacement of a halide ligand, probably by two groups on the enzyme, at least one of which may be a sulfur containing acid.
3 citations