Abstract
A series of new heteroleptic cationic (η7-cycloheptatrienyl)(η5-cyclopentadienyl)manganese(I) (“tromancenium”) sandwich complexes containing the cycloheptatrienyl ligand and various sterically bulky cyclopentadienyl ligands was synthesized in a one-pot two-step procedure via their cymantrene precursors by high-power LED photochemistry followed by oxidation. In comparison to their less-substituted congeners which display only partially reversible redox events, these new air-stable tromancenium salts show reversible Mn(I)/Mn(II) and quasi-reversible Mn(I)/Mn(0) redox couples, as intended by the conceptual design of this work. Full spectroscopic and structural characterization of by 1H, 13C, 55Mn NMR, IR, UV–vis spectroscopy, high-resolution mass spectrometry and single crystal structure analysis is reported.
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