UC Santa Barbara

The reactivity of the "masked" terminal nickel sulfide complex, [K(18-crown-6)][(L(tBu))Ni(II)(S)] (L(tBu) = {(2,6-(i)Pr2C6H3)NC((t)Bu)}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:η(2)-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.