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


Frech, C M; Ben-David, Y; Weiner, L; Milstein, D (2006). Metal-controlled reactivity of a pincer-type, sigma-coordinated naphthyl radical anion. Journal of the American Chemical Society, 128(22):7128-7129.

Abstract

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.

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.

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18 citations in Web of Science®
18 citations in Scopus®
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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:7 June 2006
Deposited On:11 Feb 2008 12:25
Last Modified:05 Apr 2016 12:20
Publisher:American Chemical Society
ISSN:0002-7863
Publisher DOI:10.1021/ja0615066
Related URLs:http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/ja0615066
PubMed ID:16734443

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