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

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

Fingerprint

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Cite this

Frech, C. M., Ben-David, Y., Weiner, L., & Milstein, D. (2006). Metal-controlled reactivity of a pincer-type, σ-coordinated naphthyl radical anion. Journal of the American Chemical Society, 128(22), 7128-7129. https://doi.org/10.1021/ja0615066

@article{629285758d594d2c8ab9ba3dfcb9028b,

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

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.",

author = "Frech, {Christian M.} and Yehoshoa Ben-David and Lev Weiner and David Milstein",

year = "2006",

month = jun

day = "7",

doi = "10.1021/ja0615066",

language = "English",

volume = "128",

pages = "7128--7129",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "22",

}

TY - JOUR

T1 - Metal-controlled reactivity of a pincer-type, σ-coordinated naphthyl radical anion

AU - Frech, Christian M.

AU - Ben-David, Yehoshoa

AU - Weiner, Lev

AU - Milstein, David

PY - 2006/6/7

Y1 - 2006/6/7

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.

UR - http://www.scopus.com/inward/record.url?scp=33744942359&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33744942359&partnerID=8YFLogxK

U2 - 10.1021/ja0615066

DO - 10.1021/ja0615066

M3 - Article

C2 - 16734443

AN - SCOPUS:33744942359

VL - 128

SP - 7128

EP - 7129

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 22

ER -

Access to Document

10.1021/ja0615066