The structural and spectroscopic characterisation of three actinyl complexes with coordinated and uncoordinated perrhenate: [UO2(ReO4)2(TPPO)3], [[(UO2)(TPPO)3]2(mu2-O2)][ReO4]2 and [NpO2(TPPO)4][ReO4

Dalton Transactions : an International Journal of Inorganic Chemistry
Gordon H JohnJames D McKinney

Abstract

The first structural characterization of an actinide complex with coordinated perrhenate is reported, [UO2(ReO4)2(TPPO)3] (1). In this [UO2]2+ complex two [ReO4]- anions and three TPPO (triphenylphosphine oxide) P=O donor ligands are coordinated in the equatorial plane in a cisoid arrangement. This bonding arrangement, and apparent strain observed in the equatorially bonded ligands, is attributed to the solid state packing in adjacent molecules in which hydrophobic TPPO ligands form an effective "shell" around a hydrophilic core of two UO2(ReO4)2 moieties. Solid state vibrational spectroscopy (infrared and Raman), 31P CP MAS NMR and elemental analysis are also consistent with the formula of 1. Solution state vibrational spectroscopy and 31P NMR measurements in EtOH indicate the lability of the TPPO and [ReO4]- groups. The photolytic generation of peroxide in EtOH solutions of 1 leads to the formation of trace quantities of [[(UO2)(TPPO)3]2(mu2-O2)][ReO4]2, 2, in which the coordinated [ReO4]- groups of 1 have been displaced by bridging O2(2-), derived from atmospheric O2. Finally, attempts to synthesise a [NpO2]+ analogue of have resulted only in the formation of [NpO2(TPPO)4][ReO4], 3, in which [ReO4]- acts solely as a counter ...Continue Reading

Citations

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May 18, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Sokratis T TsantisSpyros P Perlepes
May 24, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Michel Ephritikhine
Dec 6, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Andrew D SuttonMadeleine Helliwell
Apr 12, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Gordon H JohnMadeleine Helliwell
Nov 19, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Isabel S GonçalvesCarlos C Romão
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