Reactivity of a Nickel Sulfide with Carbon Monoxide and Nitric Oxide

Article abstract of DOI:10.1021/jacs.6b08084

The reactivity of the "masked" terminal nickel sulfide complex, [K(18-crown-6)][(L^tBu)Ni^II(S)] (L^tBu = {(2,6-ⁱPr₂C₆H₃)NC(^tBu)}₂CH), with the biologically important small molecules CO and NO, was surveyed. [K(18-crown-6)][(L^tBu)Ni^II(S)] reacts with carbon monoxide (CO) via addition across the Ni-S bond to give a carbonyl sulfide complex, [K(18-crown-6)][(L^tBu)Ni^II(S,C:β²-COS)] (1). Additionally, [K(18-crown-6)][(L^tBu)Ni^II(S)] reacts with nitric oxide (NO) to yield a nickel nitrosyl, [(L^tBu)Ni(NO)] (2), and a perthionitrite anion, [K(18-crown-6)][SSNO] (3). The isolation of 3 from this reaction confirms, for the first time, that transition metal sulfides can react with NO to form the biologically important [SSNO]^· anion.