NDLI: Redox properties and electron transfer in a triarylamine-substituted HS-Co<sup>2+</sup>/LS-Co<sup>3+</sup> redox couple

Content Provider	Royal Society of Chemistry (RSC)
Author	Korb, Marcus Petzold, Holm Schnaubelt, Linda Dmitrieva, Evgenia Speck, J. Matthäus Rosenkranz, Marco
Copyright Year	2017
Abstract	A new tridentate phenanthroline-pyridyl-based ligand 1 containing a redox active Tara (triaryl amine) unit has been developed (1 = 4-((6-(1,10-phenanthrolin-2-yl)pyridin-2-yl)oxy)-N,N-di-p-tolylaniline). The complex [Co2+(1)2](ClO4/BF4)2 was prepared and the order of the oxidation steps was analysed by cyclic voltammetry and EPR/UV-vis-NIR spectroelectrochemistry. Oxidation of [Co2+(1)2]2+ to [Co3+(1+)2]5+ proceeds in two steps. The first step is the Co2+/3+ centred oxidation to [Co3+(1)2]3+ (E°′(M2+/3+) = 284 mV vs. Fc/Fc+) followed by oxidation of the Tara0/+ centres (E°′(Tara) = 531 mV). Both kinds of oxidation processes were independently investigated in the analogous complexes [Zn(1)2](ClO4)2 and [Co(2)2](BF4)2 allowing an assignment of changes in the electronic spectra to the redox states (2 = 2-(6-phenoxypyridin-2-yl)-1,10-phenanthroline). Although spectroelectrochemistry did not indicate substantial coupling between the redox centres the Tara unit is an efficient mediator for the self-exchange in the [Co2+/3+(1)2]2+/3+ couple. The electron transfer by self-exchange in [Co2+/3+(1)2]2+/3+ was further investigated by variable temperature (VT) 1H NMR spectroscopy. In addition, the resonances found in the paramagnetic proton NMR spectra were assigned by using COSY, T1 and EXSY measurements in combination with the Co–N distances obtained from X-ray analysis. [Co(1)2]2+ is found in the HS state. In contrast, the Fe2+ species [Fe(1)2](ClO4)2 is a spincrossover system. The SCO was analysed in solution by VT 1H NMR and VT/vis spectroscopy.
Starting Page	2690
Ending Page	2698
Page Count	9
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	46
Issue Number	8
Journal	Dalton Transactions
DOI	10.1039/c6dt04748c
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	SCO Tara Ligand Redox Cyclic voltammetry Ferrocenium tetrafluoroborate Phenanthroline Nuclear magnetic resonance spectroscopy Paramagnetism Proton nuclear magnetic resonance X-ray crystallography Nuclear magnetic resonance Willem C. Vis Moot Spectroscopy
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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