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Reactivity of a Nickel Sulfide with Carbon Monoxide and Nitric Oxide

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posted on 2016-09-08, 00:00 authored by Nathaniel J. Hartmann, Guang Wu, Trevor W. Hayton
The reactivity of the “masked” terminal nickel sulfide complex, [K­(18-crown-6)]­[(LtBu)­NiII(S)] (LtBu = {(2,6-iPr2C6H3)­NC­(tBu)}2CH), with the biologically important small molecules CO and NO, was surveyed. [K­(18-crown-6)]­[(LtBu)­NiII(S)] reacts with carbon monoxide (CO) via addition across the Ni–S bond to give a carbonyl sulfide complex, [K­(18-crown-6)]­[(LtBu)­NiII(S,C2-COS)] (1). Additionally, [K­(18-crown-6)]­[(LtBu)­NiII(S)] reacts with nitric oxide (NO) to yield a nickel nitrosyl, [(LtBu)­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.