Reductions of challenging organic substrates by a nickel complex of a noninnocent crown carbene ligand.
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.
Findlay
Neil J
NJ
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, United Kingdom.
Park
Stuart R
SR
Schoenebeck
Franziska
F
Cahard
Elise
E
Zhou
Sheng-Ze
SZ
Berlouis
Leonard E A
LE
Spicer
Mark D
MD
Tuttle
Tell
T
Murphy
John A
JA