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Journal of the American Chemical Society, 22 Reduction of the new, naphthalene-based pincer complex [ C10H5 CH2PiPr2 2 Rh 1-N2 ] with potassium metal gave the corresponding -coordinated naphthyl radical anion complex, with a ring-centered radical and no change in the formal metal oxidation state.

Abstract paper no. 59

This paramagnetic complex can be reoxidized to the diamagnetic one with [Cp2Fe][BF4], the structural integrity being retained. Unexpectedly, treatment of a THF solution of the reduced complex with water leads to the immediate evolution of dihydrogen, with reoxidation to the starting complex. This is in striking contrast with the well-known reactivity of the naphthide radical anion, which undergoes ring protonation by water to form 1,4-dihydronaphthalene and naphthalene in a ratio.

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  6. Metal-controlled reactivity of a pincer-type, sigma-coordinated naphthyl radical anion.

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Metal-controlled reactivity of a pincer-type, sigma-coordinated naphthyl radical anion

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