Synthesis and reactivity of a nickel(ii) thioperoxide complex: demonstration of sulfide-mediated N2O reduction†,Chemical Science

当前位置： X-MOL 学术 › Chem. Sci. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Synthesis and reactivity of a nickel(ii) thioperoxide complex: demonstration of sulfide-mediated N2O reduction†
Chemical Science ( IF 7.6 ) Pub Date : 2018-06-27 00:00:00 , DOI: 10.1039/c8sc02536c
Nathaniel J Hartmann ₁ , Guang Wu ₁ , Trevor W Hayton ₁

Affiliation

The thiohyponitrite ([SNNO]²⁻) complex, [K(18-crown-6)][L^tBuNi^II(κ²-SNNO)] (L^tBu = {(2,6-ⁱPr₂C₆H₃)NC(^tBu)}₂CH), extrudes N₂ under mild heating to yield [K(18-crown-6)][L^tBuNi^II(η²-SO)] (1), along with minor products [K(18-crown-6)][L^tBuNi^II(η²-OSSO)] (2) and [K(18-crown-6)][L^tBuNi^II(η²-S₂)] (3). Subsequent reaction of 1 with carbon monoxide (CO) results in the formation of [K(18-crown-6)][L^tBuNi^II(η²-SCO)] (4), [K(18-crown-6)][L^tBuNi^II(S,O:κ²-SCO₂)] (5), [K(18-crown-6)][L^tBuNi^II(κ²-CO₃)] (6), carbonyl sulfide (COS) (7), and [K(18-crown-6)][L^tBuNi^II(S₂CO)] (8). To rationalize the formation of these products we propose that 1 first reacts with CO to form [K(18-crown-6)][L^tBuNi^II(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)][L^tBuNi^II(κ²-SOCO₂)] (11). The Ni(II) monothiopercarbonate subsequently transfers a S-atom to CO to form COS and [K(18-crown-6)][L^tBuNi^II(κ²-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)][L^tBuNi^II(κ²-SNNO)] to 1 and then I, which represents the formal reduction of N₂O by CO.

中文翻译：

镍 (ii) 硫过氧化物络合物的合成和反应性：硫化物介导的 N2O 还原的示范†

硫代次亚硝酸盐 ([SNNO] ^2- ) 络合物 [K(18-crown-6)][L ^{t Bu} Ni ^II (κ ² -SNNO)] (L ^{t Bu} = {(2,6- ⁱ Pr ₂ C ₆ H ₃ )NC( ^t Bu)} ₂ CH)，在温和加热下挤出 N ₂得到 [K(18-crown-6)][L ^{t Bu} Ni ^II (η ² -SO)] ( 1 )，以及次要产品 [K(18-crown-6)][L ^{t Bu} Ni ^II (η ² -OSSO)] ( 2) 和 [K(18-crown-6)][L ^{t Bu} Ni ^II (η ² -S ₂ )] ( 3 )。1与一氧化碳 (CO) 的后续反应导致形成 [K(18-crown-6)][L ^{t Bu} Ni ^II (η ² -SCO)] ( 4 ), [K(18-crown-6) )][L ^{t Bu} Ni ^II ( S , O :κ ² -SCO ₂ )] ( 5 ), [K(18-crown-6)][L ^{t Bu} Ni ^II (κ ² -CO ₃ )] (6 )、羰基硫(COS) ( 7 )和[K(18-crown-6)][L ^{t Bu} Ni ^II (S ₂ CO)] ( 8 )。为了使这些产物的形成合理化，我们建议1首先通过O 原子抽象与 CO 反应形成 [K(18-crown-6)][L ^{t Bu} Ni ^II (S)] ( I ) 和 CO _{2 。}随后，配合物I与 CO 或 CO ₂反应分别形成4和5。同样，形成络合物6和 COS 可以通过1与 CO ₂反应形成推定的 Ni( II ) 单硫代过碳酸酯 [K(18-crown-6)][L ^{t Bu} Ni ^II (κ ² -SOCO ₂ )] ( 11 )来合理化. Ni( II ) 单硫代过碳酸酯随后将 S 原子转移到 CO 以形成 COS 和 [K(18-crown-6)][L ^{t Bu} Ni ^II (κ ² -CO ₃ )] ( 6 )。最后，8的形成可以通过 COS 与I的反应来合理化。至关重要的是，观察配合物反应混合物中的图4和5揭示了 [K(18-crown-6)][L ^{t Bu} Ni ^II (κ ² -SNNO)] 逐步转化为1然后是I，这代表 N ₂ O的正式还原由 CO.

更新日期：2018-06-27

点击分享查看原文

点击收藏

公开下载

阅读更多本刊最新论文本刊介绍/投稿指南11