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Issue 3, 2020
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Dicerium letterbox-shaped tetraphenolates: f-block complexes designed for two-electron chemistry

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Abstract

Rare examples of molecular, dinuclear CeIII and PrIII complexes with robust Ln-coordination are accessible by use of the tetraphenolate pTP as a supporting, chelating O-donor ligand platform, pTP = [{2-(OC6H2R2-2,4)2CH}-C6H4-1,4]4− that favours the higher formal oxidation states accessible to rare earths. Two classes of complexes have been made from the platforms; one metallacyclic 2 + 2 [Ln2(pTP)2] framework with a rigid, letterbox-shaped geometry and [Ln(aryloxide)4] core, and one more flexible [(LnX)2(pTP)] with one rare earth ion at either end of the platform. The LnIII letterbox complexes have two K+ counter-cations, one of which sits inside the letterbox, binding the two central arenes of the platform sufficiently strongly that it cannot be displaced by solvent molecules (THF and pyridine) or crown ethers. Oxidation of the CeIII lettterboxes is facile and forms the unusual neutral molecular (CeIV)2 letterbox in which the CeIV reduction potential is −1.83 V vs. Fc/Fc+. The electronic structure of the Ce(III/IV) complexes was investigated using HERFD-XAS (high energy resolution fluorescence detection X-ray absorption spectroscopy).

Graphical abstract: Dicerium letterbox-shaped tetraphenolates: f-block complexes designed for two-electron chemistry

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Supplementary files

Article information


Submitted
13 Aug 2019
Accepted
29 Nov 2019
First published
20 Dec 2019

This article is Open Access

Dalton Trans., 2020,49, 877-884
Article type
Paper

Dicerium letterbox-shaped tetraphenolates: f-block complexes designed for two-electron chemistry

P. L. Arnold, K. Wang, S. J. Gray, L. M. Moreau, C. H. Booth, M. Curcio, J. A. L. Wells and A. M. Z. Slawin, Dalton Trans., 2020, 49, 877
DOI: 10.1039/C9DT03291F

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