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

doi:10.1021/ja107703n

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

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

65 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 language	English
Pages (from-to)	15462-15464
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	132
Issue number	44
DOIs	https://doi.org/10.1021/ja107703n
Publication status	Published - 10 Nov 2010

Keywords

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

Access to Document

10.1021/ja107703n

Applications and Development of Methodologies for Designing Hybrid Catalysts.
Tuttle, T. (Principal Investigator)
EPSRC (Engineering and Physical Sciences Research Council)
19/09/08 → 18/09/11
Project: Research
Physical Organic Chemistry: Opportunities In Synthesis, Materials And Pharmaceuticals (Science And Innovation Award)
Murphy, J. (Principal Investigator), Coombs, G. (Co-investigator), Ferguson, A. (Co-investigator) & Florence, A. (Co-investigator)
Scottish Funding Council SFC, EPSRC (Engineering and Physical Sciences Research Council)
1/09/07 → 30/10/12
Project: Research
New horizons in organic electron transfer
Murphy, J. (Principal Investigator)
EPSRC (Engineering and Physical Sciences Research Council)
1/10/06 → 30/09/09
Project: Research

Cite this

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title = "Reductions of challenging organic substrates by a nickel complex of a noninnocent crown carbene ligand",

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.",

keywords = "metal-ammonia reduction, super-electron-donor, pinacol coupling reaction, aromatic-compounds, aryl iodides, aldehydes, cleavage, behavior",

author = "Neil Findlay and Park, {Stuart Robert} and Franziska Schoenebeck and Elise Cahard and Sheng-Ze Zhou and Leonard Berlouis and Mark Spicer and Tell Tuttle and John Murphy",

year = "2010",

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day = "10",

doi = "10.1021/ja107703n",

language = "English",

volume = "132",

pages = "15462--15464",

journal = "Journal of the American Chemical Society",

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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

PY - 2010/11/10

Y1 - 2010/11/10

N2 - 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.

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

U2 - 10.1021/ja107703n

DO - 10.1021/ja107703n

M3 - Article

SN - 0002-7863

VL - 132

SP - 15462

EP - 15464

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 44

ER -

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

Abstract

Keywords

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Projects

Applications and Development of Methodologies for Designing Hybrid Catalysts.

Physical Organic Chemistry: Opportunities In Synthesis, Materials And Pharmaceuticals (Science And Innovation Award)

New horizons in organic electron transfer

Cite this