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

Christian M. Frech; Yehoshoa Ben-David; Lev Weiner; David Milstein

doi:10.1021/ja0615066

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

Christian M. Frech, Yehoshoa Ben-David, Lev Weiner, David Milstein

Weizmann Institute of Science, Israel

Research output: Contribution to journal › Article › peer-review

21 Citations (Scopus)

Abstract

Reduction of the new, naphthalene-based pincer complex [(C₁₀H₅(CH₂PⁱPr₂)₂)Rh(η¹-N₂)] with potassium metal gave the corresponding σ-coordinated naphthyl radical anion complex, with a ring-centered radical and no change in the formal metal oxidation state. 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 1:1 ratio.

Original language	English
Pages (from-to)	7128-7129
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	128
Issue number	22
DOIs	https://doi.org/10.1021/ja0615066
Publication status	Published - Jun 7 2006

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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abstract = "Reduction of the new, naphthalene-based pincer complex [(C10H5(CH2PiPr2)2)Rh(η1-N2)] with potassium metal gave the corresponding σ-coordinated naphthyl radical anion complex, with a ring-centered radical and no change in the formal metal oxidation state. 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 1:1 ratio.",

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AU - Frech, Christian M.

AU - Ben-David, Yehoshoa

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AU - Milstein, David

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N2 - Reduction of the new, naphthalene-based pincer complex [(C10H5(CH2PiPr2)2)Rh(η1-N2)] with potassium metal gave the corresponding σ-coordinated naphthyl radical anion complex, with a ring-centered radical and no change in the formal metal oxidation state. 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 1:1 ratio.

AB - Reduction of the new, naphthalene-based pincer complex [(C10H5(CH2PiPr2)2)Rh(η1-N2)] with potassium metal gave the corresponding σ-coordinated naphthyl radical anion complex, with a ring-centered radical and no change in the formal metal oxidation state. 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 1:1 ratio.

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