(Electro)chemical N2 Splitting by a Molybdenum Complex with an Anionic PNP Pincer-Type Ligand

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY ACS Organic & Inorganic Au Pub Date : 2024-03-04 DOI:10.1021/acsorginorgau.3c00056
Nils Ostermann, Nils Rotthowe, A. Claudia Stückl and Inke Siewert*, 
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Abstract

Molybdenum(III) complexes bearing pincer-type ligands are well-known catalysts for N2-to-NH3 reduction. We investigated herein the impact of an anionic PNP pincer-type ligand in a Mo(III) complex on the (electro)chemical N2 splitting ([LMoCl3], 1, LH = 2,6-bis((di-tert-butylphosphaneyl)methyl)-pyridin-4-one). The increased electron-donating properties of the anionic ligand should lead to a stronger degree of N2 activation. The catalyst is indeed active in N2-to-NH3 conversion utilizing the proton-coupled electron transfer reagent SmI2/ethylene glycol. The corresponding Mo(V) nitrido complex 2H exhibits similar catalytic activity as 1H and thus could represent a viable intermediate. The Mo(IV) nitrido complex 3 is also accessible by electrochemical reduction of 1 under a N2 atmosphere. IR- and UV/vis-SEC measurements suggest that N2 splitting occurs via formation of an “overreduced” but more stable [(L(N2)2Mo0)2μ-N2]2– dimer. In line with this, the yield in the nitrido complex increases with lower applied potentials.

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(钼配合物与阴离子 PNP 钳型配体的(电)化学 N2 裂解作用
带有钳型配体的钼(III)配合物是众所周知的 N2 到 NH3 还原催化剂。我们在此研究了钼(III)配合物中的阴离子 PNP 钳型配体对 N2(电)化学拆分([LMoCl3]-, 1-, LH = 2,6-双((二叔丁基膦烷基)甲基)-吡啶-4-酮)的影响。阴离子配体的电子供能特性的增强应导致更强的 N2 活化程度。利用质子耦合电子转移试剂 SmI2/乙二醇,该催化剂在 N2 到 NH3 的转化过程中确实具有活性。相应的 Mo(V)吡啶络合物 2H 表现出与 1H 类似的催化活性,因此可能是一种可行的中间体。在氮气环境下,通过电化学还原 1-,也可以得到钼(IV)吡啶配合物 3-。IR- 和 UV/vis-SEC 测量结果表明,N2 分离是通过形成 "过度还原 "但更稳定的 [(L(N2)2Mo0)2μ-N2]2- 二聚体来实现的。与此相一致的是,随着应用电位的降低,氮化物复合物的产率也会增加。
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ACS Organic & Inorganic Au
ACS Organic & Inorganic Au 有机化学、无机化学-
CiteScore
4.10
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期刊介绍: ACS Organic & Inorganic Au is an open access journal that publishes original experimental and theoretical/computational studies on organic organometallic inorganic crystal growth and engineering and organic process chemistry. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Organic chemistry Organometallic chemistry Inorganic Chemistry and Organic Process Chemistry.
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