Reactivity of a Nickel Sulfide with Carbon Monoxide and Nitric Oxide

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:η²-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.