Dangling thiyl radical: Stabilized in [PPh_4]_2[(bdt) W~(VI)(O)(μ-S)_2Cu~I(SC_6H _4S?)]

摘要

The synthesis, crystal structure, and spectroscopic characterization of [PPh_4]_2[(bdt)W(O)(S_2)Cu(SC_6H _4S?)] (3; bdt = benzenedithiolate) relevant to the active site of carbon monoxide dehydrogenase are presented. Curiously, in 3, the copper(I) benzenemonothiolate subcenter possesses a dangling thiyl radical that is stabilized by a disulfido-bridged oxo tungsten dithiolene core. The benzenedithiolate ligand, which is generally bidentate in nature, acts as a bidentate and also as a monodentate in 3. The formation of an unusual dangling thiyl radical has been magnetically and spectroscopically identified and has been supported by the density functional theory level of calculation.