KOtBu: a privileged reagent for electron transfer reactions?

Joshua P. Barham, Graeme Coulthard, Katie J. Emery, Eswararao Doni, Florimond Cumine, Giuseppe Nocera, Matthew P. John, Leonard E. A. Berlouis, Thomas McGuire, Tell Tuttle, John A. Murphy

Research output: Contribution to journalArticle

105 Citations (Scopus)

Abstract

Many recent studies have used KOtBu in organic reactions that involve single electron transfer; in the literature, the electron transfer is proposed to occur either directly from the metal alkoxide or indirectly, following reaction of the alkoxide with a solvent or additive. These reaction classes include coupling reactions of halobenzenes and arenes, reductive cleavages of dithianes and SRN1 reactions. Direct electron transfer would imply that alkali metal alkoxides are willing partners in these electron transfer reactions, but the literature reports provide little or no experimental evidence for this. This paper examines each of these classes of reaction in turn, and contests the roles proposed for KOtBu; instead, it provides new mechanistic information that in each case supports the in situ formation of organic electron donors. We go on to show that direct electron transfer from KOtBu can however occur in appropriate cases, where the electron acceptor has a reduction potential near the oxidation potential of KOtBu, and the example that we use is CBr4. In this case, computational results support electrochemical data in backing a direct electron transfer reaction.
LanguageEnglish
Pages7402-7410
Number of pages9
JournalJournal of the American Chemical Society
Volume138
Issue number23
Early online date16 May 2016
DOIs
Publication statusPublished - 15 Jun 2016

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Electrons
Alkali Metals
Alkali metals
Metals
Oxidation

Keywords

  • KOtBu
  • electron transfer
  • alkoxide
  • organic electron donors

Cite this

Barham, Joshua P. ; Coulthard, Graeme ; Emery, Katie J. ; Doni, Eswararao ; Cumine, Florimond ; Nocera, Giuseppe ; John, Matthew P. ; Berlouis, Leonard E. A. ; McGuire, Thomas ; Tuttle, Tell ; Murphy, John A. / KOtBu : a privileged reagent for electron transfer reactions?. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 23. pp. 7402-7410.
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KOtBu : a privileged reagent for electron transfer reactions? / Barham, Joshua P.; Coulthard, Graeme; Emery, Katie J.; Doni, Eswararao; Cumine, Florimond; Nocera, Giuseppe; John, Matthew P.; Berlouis, Leonard E. A.; McGuire, Thomas; Tuttle, Tell; Murphy, John A.

In: Journal of the American Chemical Society, Vol. 138, No. 23, 15.06.2016, p. 7402-7410.

Research output: Contribution to journalArticle

TY - JOUR

T1 - KOtBu

T2 - Journal of the American Chemical Society

AU - Barham, Joshua P.

AU - Coulthard, Graeme

AU - Emery, Katie J.

AU - Doni, Eswararao

AU - Cumine, Florimond

AU - Nocera, Giuseppe

AU - John, Matthew P.

AU - Berlouis, Leonard E. A.

AU - McGuire, Thomas

AU - Tuttle, Tell

AU - Murphy, John A.

PY - 2016/6/15

Y1 - 2016/6/15

N2 - Many recent studies have used KOtBu in organic reactions that involve single electron transfer; in the literature, the electron transfer is proposed to occur either directly from the metal alkoxide or indirectly, following reaction of the alkoxide with a solvent or additive. These reaction classes include coupling reactions of halobenzenes and arenes, reductive cleavages of dithianes and SRN1 reactions. Direct electron transfer would imply that alkali metal alkoxides are willing partners in these electron transfer reactions, but the literature reports provide little or no experimental evidence for this. This paper examines each of these classes of reaction in turn, and contests the roles proposed for KOtBu; instead, it provides new mechanistic information that in each case supports the in situ formation of organic electron donors. We go on to show that direct electron transfer from KOtBu can however occur in appropriate cases, where the electron acceptor has a reduction potential near the oxidation potential of KOtBu, and the example that we use is CBr4. In this case, computational results support electrochemical data in backing a direct electron transfer reaction.

AB - Many recent studies have used KOtBu in organic reactions that involve single electron transfer; in the literature, the electron transfer is proposed to occur either directly from the metal alkoxide or indirectly, following reaction of the alkoxide with a solvent or additive. These reaction classes include coupling reactions of halobenzenes and arenes, reductive cleavages of dithianes and SRN1 reactions. Direct electron transfer would imply that alkali metal alkoxides are willing partners in these electron transfer reactions, but the literature reports provide little or no experimental evidence for this. This paper examines each of these classes of reaction in turn, and contests the roles proposed for KOtBu; instead, it provides new mechanistic information that in each case supports the in situ formation of organic electron donors. We go on to show that direct electron transfer from KOtBu can however occur in appropriate cases, where the electron acceptor has a reduction potential near the oxidation potential of KOtBu, and the example that we use is CBr4. In this case, computational results support electrochemical data in backing a direct electron transfer reaction.

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