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钨配合物介导的氮气化学催化转化为氨

Chemocatalytic Conversion of Dinitrogen to Ammonia Mediated by a Tungsten Complex.

作者信息

Vogt Anna-Marlene, Engesser Tobias A, Krahmer Jan, Michaelis Niels, Pfeil Mareike, Junge Jannik, Näther Christian, Le Poul Nicolas, Tuczek Felix

机构信息

Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, 24118, Kiel, Germany.

Univ. Brest, CNRS, UMR 6521, F 29200, Brest, France.

出版信息

Angew Chem Int Ed Engl. 2025 Feb 10;64(7):e202420220. doi: 10.1002/anie.202420220. Epub 2025 Jan 13.

DOI:10.1002/anie.202420220
PMID:39688523
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11811599/
Abstract

Whereas molybdenum dinitrogen complexes have played a major role as catalytic model systems of nitrogenase, corresponding tungsten complexes were in most cases found to be catalytically inactive. Herein, we present a modified pentadentate tetrapodal (pentaPod) phosphine ligand in which two dimethylphosphine groups of the pentaPod (P5) ligand have been replaced with phospholanes (Pln). The derived molybdenum complex [Mo(N)P5] generates 22 and the analogous tungsten complex [W(N)P5] 7 equivalents of NH from N in the presence of 180 equivalents of SmI(THF)/HO, rendering the latter the first tungsten complex chemocatalytically converting N to NH. In contrast, the tungsten complex [W(N)P5] generates ammonia from N only in a slightly overstoichiometric fashion. The reasons for these reactivity differences are investigated with the help of spectroscopic and electrochemical methods.

摘要

虽然钼二氮配合物作为固氮酶的催化模型体系发挥了重要作用，但在大多数情况下，相应的钨配合物被发现没有催化活性。在此，我们展示了一种经过修饰的五齿四足（pentaPod）膦配体，其中pentaPod（P5）配体的两个二甲基膦基团已被膦烷（Pln）取代。衍生的钼配合物[Mo(N)P5]在180当量的SmI(THF)/HO存在下，从N生成22当量的NH，类似的钨配合物[W(N)P5]生成7当量的NH，使后者成为第一个将N化学催化转化为NH的钨配合物。相比之下，钨配合物[W(N)P5]仅以略超化学计量的方式从N生成氨。借助光谱和电化学方法研究了这些反应性差异的原因。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/ac1ed06e2d19/ANIE-64-e202420220-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/8360a167cd5d/ANIE-64-e202420220-g001.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/cc9d33465e74/ANIE-64-e202420220-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/257166099673/ANIE-64-e202420220-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/2e8de76b9744/ANIE-64-e202420220-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/ae39a3e2d487/ANIE-64-e202420220-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/a745ff3bc82c/ANIE-64-e202420220-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/3b330f53bef2/ANIE-64-e202420220-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/9049adea203c/ANIE-64-e202420220-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/ac1ed06e2d19/ANIE-64-e202420220-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/8360a167cd5d/ANIE-64-e202420220-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/4b9a1d16bb0d/ANIE-64-e202420220-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/cc9d33465e74/ANIE-64-e202420220-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/257166099673/ANIE-64-e202420220-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/2e8de76b9744/ANIE-64-e202420220-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/ae39a3e2d487/ANIE-64-e202420220-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/a745ff3bc82c/ANIE-64-e202420220-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/3b330f53bef2/ANIE-64-e202420220-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/9049adea203c/ANIE-64-e202420220-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb60/11811599/ac1ed06e2d19/ANIE-64-e202420220-g012.jpg

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