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 | |
| Publication status | Published - Jun 7 2006 |
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Metal-controlled reactivity of a pincer-type, σ-coordinated naphthyl radical anion. / Frech, Christian M.; Ben-David, Yehoshoa; Weiner, Lev; Milstein, David.
In: Journal of the American Chemical Society, Vol. 128, No. 22, 07.06.2006, p. 7128-7129.Research output: Contribution to journal › Article
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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 -