Journal
DALTON TRANSACTIONS
Volume 43, Issue 17, Pages 6513-6524Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4dt00341a
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- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1039925] Funding Source: National Science Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0822838, 1362127] Funding Source: National Science Foundation
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An unexpected doubling in redox storage emerging from a new pincer ligand upon bis-ligation of iron(II) is described. When tetrazine arms are present at the two ortho positions of pyridine, the resulting bis-tetrazinyl pyridine (btzp) pincer ligand displays a single one-electron reduction at ca. -0.85 V vs. Ag/AgCl. Complexation to iron, giving the cation Fe( btzp) 2(2+), shows no oxidation but four reduction waves in cyclic voltammetry instead of the two expected for the two constituent ligands. Mossbauer, X-ray diffraction and NMR studies show the iron species to contain low spin Fe( II), but with evidence of back donation from iron to the pincer ligands. CV and UV-Vis spectroelectrochemistry, as well as titration studies as monitored by CV, electronic spectra and EPR reveal the chemical reversibility of forming the reduced species. DFT and EPR studies show varying degrees of delocalization of unpaired spin in different species, including that of a btzp(-1) radical anion, partnered with various cations.
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