Issue 7, 2016

Covalency hinders AnO2(H2O)+ → AnO(OH)2+ isomerisation (An = Pa–Pu)

Abstract

The enthalpies of the reactions AnO2+ → AnO+ + O and AnO2+ + H2O → AnO2(H2O)+, and those of the isomerisation of the latter to AnO(OH)2+, have been calculated for An = Pa–Pu. The data match previous experimental and computational values very closely, and the computed enthalpy for the isomerisation of PaO2(H2O)+ to PaO(OH)2+, requested by the authors of Inorg. Chem., 2015, 54, 7474, is found to be 0.8 kJ mol−1. The NPA, NBO and QTAIM approaches are used to probe covalency in the An–Oyl bond of AnO2(H2O)+, and all metrics agree that these bonds become increasingly covalent as the 5f series is crossed, providing rationalisation for the increasingly endothermic isomerisation reactions. QTAIM analysis indicates that the An[double bond, length as m-dash]O and An–OH bonds in the oxide hydroxide isomers also become increasingly covalent as the 5f series is crossed.

Graphical abstract: Covalency hinders AnO2(H2O)+ → AnO(OH)2+ isomerisation (An = Pa–Pu)

Supplementary files

Article information

Article type
Paper
Submitted
02 Nov 2015
Accepted
07 Jan 2016
First published
07 Jan 2016

Dalton Trans., 2016,45, 3158-3162

Author version available

Covalency hinders AnO2(H2O)+ → AnO(OH)2+ isomerisation (An = Pa–Pu)

N. Kaltsoyannis, Dalton Trans., 2016, 45, 3158 DOI: 10.1039/C5DT04317D

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