Low Temperature Spectroscopic Study of the Sulfides Binding by Dioxygen Adduct of Cobalt Porphyrin

摘要

The interaction of dimethyl sulfide ((CH3)(2)S) and hydrogen sulfide (H2S) with cobalt porphyrin and its five-coordinate dioxygen complex was studied at low temperatures in sublimated porphyrin layers using electronic and infrared absorption spectroscopy. Upon addition of sulfides to a cryostat containing Co(TTP)O-2 (TTP is meso-letratolylporphyrinato dianion) at low temperatures, the FTIR and Lis electronic spectral changes were observed which are consistent with sulfide binding in axial trans-position to dioxygen. Density functional theory (DFT) computational analysis also supports formation of the six-coordinate adducts. These complexes are stable only at low temperatures and dissociate upon heating.