Reductions of challenging organic substrates by a nickel complex of a noninnocent crown carbene ligand

Neil Findlay, Stuart Robert Park, Franziska Schoenebeck, Elise Cahard, Sheng-Ze Zhou, Leonard Berlouis, Mark Spicer, Tell Tuttle, John Murphy

Research output: Contribution to journalArticle

47 Citations (Scopus)

Abstract

The first crown-tetracarbene complex of Ni(II) has been prepared, and its crystal structure determined. The complex can be reduced by Na/Hg, with an uptake of two electrons. The reduced complex reductively cleaves arenesulfonamides, including those derived from secondary aliphatic amines, and effects Birch reduction of anthracenes as well as reductive cleavage of stilbene oxides. Computational studies show that the orbital that receives electrons upon reduction of the complex 2 is predominantly based on the crown carbene ligand and also that the HOMO of the parent complex 2 is based on the ligand.
Original languageEnglish
Pages (from-to)15462-15464
Number of pages3
JournalJournal of the American Chemical Society
Volume132
Issue number44
DOIs
Publication statusPublished - 10 Nov 2010

Fingerprint

Nickel
Crowns
Anthracenes
Ligands
Electrons
Betula
Anthracene
Substrates
Amines
Crystal structure
Oxides
carbene
stilbene oxide

Keywords

  • metal-ammonia reduction
  • super-electron-donor
  • pinacol coupling reaction
  • aromatic-compounds
  • aryl iodides
  • aldehydes
  • cleavage
  • behavior

Cite this

Findlay, Neil ; Park, Stuart Robert ; Schoenebeck, Franziska ; Cahard, Elise ; Zhou, Sheng-Ze ; Berlouis, Leonard ; Spicer, Mark ; Tuttle, Tell ; Murphy, John. / Reductions of challenging organic substrates by a nickel complex of a noninnocent crown carbene ligand. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 44. pp. 15462-15464.
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Reductions of challenging organic substrates by a nickel complex of a noninnocent crown carbene ligand. / Findlay, Neil; Park, Stuart Robert; Schoenebeck, Franziska; Cahard, Elise; Zhou, Sheng-Ze; Berlouis, Leonard; Spicer, Mark; Tuttle, Tell; Murphy, John.

In: Journal of the American Chemical Society, Vol. 132, No. 44, 10.11.2010, p. 15462-15464.

Research output: Contribution to journalArticle

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T1 - Reductions of challenging organic substrates by a nickel complex of a noninnocent crown carbene ligand

AU - Findlay, Neil

AU - Park, Stuart Robert

AU - Schoenebeck, Franziska

AU - Cahard, Elise

AU - Zhou, Sheng-Ze

AU - Berlouis, Leonard

AU - Spicer, Mark

AU - Tuttle, Tell

AU - Murphy, John

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AB - The first crown-tetracarbene complex of Ni(II) has been prepared, and its crystal structure determined. The complex can be reduced by Na/Hg, with an uptake of two electrons. The reduced complex reductively cleaves arenesulfonamides, including those derived from secondary aliphatic amines, and effects Birch reduction of anthracenes as well as reductive cleavage of stilbene oxides. Computational studies show that the orbital that receives electrons upon reduction of the complex 2 is predominantly based on the crown carbene ligand and also that the HOMO of the parent complex 2 is based on the ligand.

KW - metal-ammonia reduction

KW - super-electron-donor

KW - pinacol coupling reaction

KW - aromatic-compounds

KW - aryl iodides

KW - aldehydes

KW - cleavage

KW - behavior

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