Electron-induced conversion of silylones to six-membered cyclic silylenes.
A silicon atom in the zero oxidation state stabilized by two carbene ligands is known as siladicarbene (silylone). There are two pairs of electrons on the silicon atom in silylone. This was recently confirmed by both experimental and theoretical charge density investigations. The silylone is stable up to 195 °C in an inert atmosphere. However, a substoichiometric amount (33 mol%) of potassium metal triggers the activation of the unsaturated C:Si:C backbone, leading to a selective reaction with a tertiary C-H bond in an atom-economical approach to form a six-membered cyclic silylene with three-coordinate silicon atom. Cyclic voltammetry shows that this reaction proceeds via the formation of a silylone radical anion intermediate, which is further confirmed by EPR spectroscopy.
Institut für Anorganische Chemie, Georg-August-Universität , Tammannstraße 4, 37077 Göttingen, Germany.
Sudipta
S
Roy
Kartik Chandra
KC
Mondal
Lennard
L
Krause
Peter
P
Stollberg
Regine
R
Herbst-Irmer
Dietmar
D
Stalke
Jann
J
Meyer
A Claudia
AC
Stückl
Bholanath
B
Maity
Debasis
D
Koley
Suresh Kumar
SK
Vasa
Sheng Qi
SQ
Xiang
Rasmus
R
Linser
Herbert W
HW
Roesky
D004583:Electrons; D015394:Molecular Structure; D011789:Quantum Theory; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry; D012825:Silicon / Q000737:chemistry
D012821:Silanes; D012825:Silicon