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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Dangling thiyl radical: stabilized in [PPh4]2[(bdt)W(VI)(O)(μ-S)2Cu(I)(SC6H4S•)]
Moumita Bose1, Golam Moula, Ameerunisha Begum
1Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India.
Abstract:
The synthesis, crystal structure, and spectroscopic characterization of [PPh(4)](2)[(bdt)W(O)(S(2))Cu(SC(6)H(4)S(•))] (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.
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