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Issue 33, 2019
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Synthesis and redox chemistry of Pd(ii) complexes of a pincer verdazyl ligand

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A series of palladium(II) complexes containing a redox-active, tridentate verdazyl ligand of general formula (verdazyl)PdL (L = Cl, CH3CN) are synthesized. The tetrazine core of tridentate verdazyl ligand 5 is flanked by two pyridyl groups, creating a geometry in which the ancillary ligand L is bound trans to the verdazyl ring in the square planar metal complexes. Pd(II) complexes were isolated with the verdazyl ligand in either its neutral radical charge state (6: L = CH3CN, 12: L = Cl) or its closed-shell monoanionic charge state (10: L = CH3CN, 9: L = Cl). The charge state of the ligand was determined using X-ray crystallography and NMR, EPR, and IR spectroscopy. The cyclic voltammograms of radical complexes 6 and 12 each contain a reversible one-electron reduction wave and an irreversible one-electron oxidation wave. The complexes can be chemically interconverted between radical ligand (6, 12) and reduced, closed-shell anion (9, 10) using decamethylferrocene as the reductant and a mixture of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and fluoroboric acid as the oxidant.

Graphical abstract: Synthesis and redox chemistry of Pd(ii) complexes of a pincer verdazyl ligand

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The article was received on 17 Jun 2019, accepted on 25 Jul 2019 and first published on 26 Jul 2019

Article type: Paper
DOI: 10.1039/C9DT02549A
Dalton Trans., 2019,48, 12674-12683

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    Synthesis and redox chemistry of Pd(II) complexes of a pincer verdazyl ligand

    C. A. Sanz, B. O. Patrick and R. G. Hicks, Dalton Trans., 2019, 48, 12674
    DOI: 10.1039/C9DT02549A

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