Reactivity of a Nickel Sulfide with Carbon Monoxide and Nitric Oxide

摘要

The reactivity of the "masked" terminal nickel sulfide complex, [K(l8-crown-6)][(L~(tBu))Ni~Ⅱ(S)] (L~(tBu)= {(2,6-~iPr_2C_6H_3)NC(~tBu)}_2CH), with the biologically important small molecules CO and NO, was surveyed. [K(l8-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(l8-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(l8-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.