Tin-centered radical and cation: stable and free.
The first stable stannyl radical (tBu2MeSi)3Sn* (1) has been synthesized by the reaction of tBu2MeSiNa with SnCl2-dioxane in diethyl ether. The X-ray crystal structure and electron paramagnetic resonance (EPR) data of this radical show that 1 has a planar geometry, being a pi-radical in both the solid and the liquid states. One-electron oxidation of 1 with Ph3C+.B(C6F5)4- in benzene quantitatively produced the corresponding cation (tBu2MeSi)3Sn+.B(C6F5)4- (2), representing the stable free stannylium ion that has been fully characterized by X-ray analysis and NMR data. Being free, 2 features a record downfield shifted resonance for stannylium ions: +2653 ppm.
Sekiguchi
Akira
A
Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan. sekiguch@staff.chem.tsukuba.ac.jp
Fukawa
Tomohide
T
Lee
Vladimir Ya
VY
Nakamoto
Masaaki
M