Tetrazine Chelate Ligands Bridging Two [Ru(acac)2] Fragments: Mixed Valency and Radical Complex Formation

Using bis(3‐methyl‐2‐pyridyl)‐1,2,4,5‐tetrazine 1, 3‐(2‐pyrimidyl)‐6‐methyl‐1,2,4,5‐tetrazine 2 and bis(2‐pyrimidyl)‐1,2,4,5‐tetrazine=bmtz as ligands, the complexes 3=[Ru(acac)2(1)], 4={[Ru(acac)2]2(1)], 5={[Ru(acac)2]2(bmtz)], and 6={[Ru(acac)2]2(2)] were prepared and identified by structure analy...

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Published in:Zeitschrift für anorganische und allgemeine Chemie (1950) Vol. 648; no. 23
Main Authors: Kaim, Wolfgang, Löw, Isabell, Ringenberg, Mark R., Schwederski, Brigitte, Filippou, Vasileios, Fiedler, Jan
Format: Journal Article
Language:English
Published: Weinheim Wiley Subscription Services, Inc 13.12.2022
Subjects:
Complex formation
Crystal structure
Crystallization
Cyclic voltammetry
Diruthenium compounds
EPR spectroscopy
Ligands
Oxidation
Spectroelectrochemistry
Structural analysis
ISSN:0044-2313, 1521-3749
Online Access:Get full text
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Summary:Using bis(3‐methyl‐2‐pyridyl)‐1,2,4,5‐tetrazine 1, 3‐(2‐pyrimidyl)‐6‐methyl‐1,2,4,5‐tetrazine 2 and bis(2‐pyrimidyl)‐1,2,4,5‐tetrazine=bmtz as ligands, the complexes 3=[Ru(acac)2(1)], 4={[Ru(acac)2]2(1)], 5={[Ru(acac)2]2(bmtz)], and 6={[Ru(acac)2]2(2)] were prepared and identified by structure analysis of crystallized material. The one‐electron oxidized form 6(PF6) was also studied structurally, suggesting a Class II mixed‐valent situation. The neutral dinuclear systems exhibit two reversible oxidation processes with comproportionation constants 109.2<Kc<1014.1 and one reduction which were analyzed UV/vis/NIR and EPR spectroscopically. Oxidation produces largely metal‐based mixed‐valent cations with very weak intervalence absorptions in the near IR whereas the electron uptake occurs at the tetrazine acceptor.
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ISSN:0044-2313
1521-3749
DOI:10.1002/zaac.202200152