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Issue 31, 2018
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Synthesis and reactivity of a nickel(ii) thioperoxide complex: demonstration of sulfide-mediated N2O reduction

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Abstract

The thiohyponitrite ([SNNO]2−) complex, [K(18-crown-6)][LtBuNiII2-SNNO)] (LtBu = {(2,6-iPr2C6H3)NC(tBu)}2CH), extrudes N2 under mild heating to yield [K(18-crown-6)][LtBuNiII2-SO)] (1), along with minor products [K(18-crown-6)][LtBuNiII2-OSSO)] (2) and [K(18-crown-6)][LtBuNiII2-S2)] (3). Subsequent reaction of 1 with carbon monoxide (CO) results in the formation of [K(18-crown-6)][LtBuNiII2-SCO)] (4), [K(18-crown-6)][LtBuNiII(S,O2-SCO2)] (5), [K(18-crown-6)][LtBuNiII2-CO3)] (6), carbonyl sulfide (COS) (7), and [K(18-crown-6)][LtBuNiII(S2CO)] (8). To rationalize the formation of these products we propose that 1 first reacts with CO to form [K(18-crown-6)][LtBuNiII(S)] (I) and CO2, via O-atom abstraction. Subsequently, complex I reacts with CO or CO2 to form 4 and 5, respectively. Similarly, the formation of complex 6 and COS can be rationalized by the reaction of 1 with CO2 to form a putative Ni(II) monothiopercarbonate, [K(18-crown-6)][LtBuNiII2-SOCO2)] (11). The Ni(II) monothiopercarbonate subsequently transfers a S-atom to CO to form COS and [K(18-crown-6)][LtBuNiII2-CO3)] (6). Finally, the formation of 8 can be rationalized by the reaction of COS with I. Critically, the observation of complexes 4 and 5 in the reaction mixture reveals the stepwise conversion of [K(18-crown-6)][LtBuNiII2-SNNO)] to 1 and then I, which represents the formal reduction of N2O by CO.

Graphical abstract: Synthesis and reactivity of a nickel(ii) thioperoxide complex: demonstration of sulfide-mediated N2O reduction

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Supplementary files

Article information


Submitted
08 Jun 2018
Accepted
26 Jun 2018
First published
27 Jun 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 6580-6588
Article type
Edge Article

Synthesis and reactivity of a nickel(II) thioperoxide complex: demonstration of sulfide-mediated N2O reduction

N. J. Hartmann, G. Wu and T. W. Hayton, Chem. Sci., 2018, 9, 6580
DOI: 10.1039/C8SC02536C

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