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New Redox-Active Iron(II) Acetylide Complex Bearing a (2-Pyridyl)aldimine Site. Synthesis and Complexation to Copper(I)
journal contribution
posted on 2020-04-03, 17:22 authored by Safaa Ibn Ghazala, Nicolas Gauthier, Frédéric Paul, Loic Toupet, Claude LapinteWe report in this contribution the isolation and characterization of a new redox-active “(η2-dppe)(η5-C5Me5)FeC⋮C-4-(C6H4)−” complex bearing a (2-pyridyl)aldimine site on the aryl ring. This new metallo
ligand, which was isolated by an unusual synthetic route from the known amino precursor complex, was
structurally characterized. In accord with its “metallo ligand” denomination, we show here that it readily
reacts with several Cu(I) precursors to form selectively, in good yields, complexes similar to those obtained
with the corresponding organic N-aryl-(2-pyridyl)aldimines. By this method, a new dinuclear Fe(II)/Cu(I) complex and a new trinuclear Fe(II)/Cu(I)/Fe(II) complex were obtained in a straightforward way
and characterized. The solid-state structure of the latter complex was also determined. Subsequently, the
redox congeners of these closed-shell compounds were generated in situ by oxidation and the electronic
structures of the open-shell parents were briefly investigated by infrared, ESR, and UV/vis spectroelectrochemistry. For instance, we conclusively show here that the mixed-valent (MV) state of the trinuclear
complex belongs to class I in the classification of Robin and Day.
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trinuclearSynthesiPyridyldppeAcetylidepyridylyielddinuclearComplexoxidationmethodaccordopen-shell parentsdenominationprecursorUVMVcontributionclassificationcharacterizationmetallo ligandredox congenersclosed-shell compoundsFeCComplexationFeBearingisolationsiteCuRedox-ActiveC 5Newspectroelectrochemistrylatterinstancecomplexredox-activearyl ringbrieflyESRSitemixed-valent