Metal-Controlled Reactivity of a Pincer-type, -Coordinated Naphthyl Radical Anion
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- 作者：Christian M. Frech ; Yehoshoa Ben-David ; Lev Weiner ; and David Milstein
- 刊名：Journal of the American Chemical Society
- 出版年：2006
- 出版时间：June 7, 2006
- 年：2006
- 卷：128
- 期：22
- 页码：7128 - 7129
- 全文大小：40K
- 年卷期：v.128,no.22(June 7, 2006)
- ISSN：1520-5126
文摘
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. 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.
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. 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.