Abstract
A 1:1 complex of a 2,6‐bis‐tetrazinylpyridine pincer ligand, btzp, with ZnCl2 is characterized. The molecule is shown to be redox active by cyclic voltammetry and by chemical reduction. The resulting monoanion loses chloride to yield a radical species [Zn(btzp)Cl] whose EPR spectrum is observed. DFT studies show that the electron added upon reduction goes into an orbital primarily comprised of tetrazine nitrogen pπ character. The Zn–Cl bonds lengthen but the Zn–Ntz bonds shorten upon reduction, in response to taking on amide character. In an alternative approach to evaluating the electron accepting capacity of btzp, the molecule [Ru(btzp)Cl2(CO)] has been fully characterized and shows a CO stretching frequency 84 cm–1 higher than that of its terpyridine analog. This result indicates btzp is strongly electron withdrawing; the CO stretching frequency for [Ru(btzp)Cl2(CO)] is among the highest ever observed for a ruthenium(II) monocarbonyl complex. Computational experiments on [Ru(btzp)Cl2(L)] test the influence of L on π‐back donation to btzp.
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