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在作为酸的一氧化碳存在下，P∩N-和As∩N-铼（I）三羰基配合物的意外氧化还原化学

Unexpected Redox Chemistry of P∩N- and As∩N-Rhenium(I) Tricarbonyl Complexes in the Presence of CO Acting as an Acid.

作者信息

Ertl Martin, Monkowius Uwe, Oppelt Kerstin T

机构信息

Linz School of Education─Chemistry, Johannes Kepler University Linz, Altenberger Strasse 69, 4040 Linz, Austria.

Department of Chemistry, University of Zürich, Winterthurerstrasse 190, 8057 Zürich, Switzerland.

出版信息

Inorg Chem. 2023 Oct 23;62(42):17510-17521. doi: 10.1021/acs.inorgchem.3c02925. Epub 2023 Oct 6.

DOI:10.1021/acs.inorgchem.3c02925
PMID:37800962
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10598882/
Abstract

This study reports on Re tricarbonyl complexes bearing 8-(diphenylphosphanyl)quinoline, P∩N, and 8-(diphenylarsanyl)quinoline, As∩N, as bidendate ligands. We studied the reactivity of these complexes in comparison with -Re(N∩N)(CO)Cl (with N∩N = 2,2'-bipyridine or 4,4'-dimethyl-2,2'-bipyridine). We used a combination of electrochemical and spectroelectrochemical methods with time-resolved spectroscopy over 10 orders of magnitude (100 ps-1 s) to investigate the peculiar reactivity of one-electron-reduced Re(CO)(P∩N)Cl and Re(CO)(As∩N)Cl complexes also in the presence of protons.

摘要

本研究报道了以8-(二苯基膦基)喹啉（P∩N）和8-(二苯基砷基)喹啉（As∩N）作为双齿配体的铼三羰基配合物。我们研究了这些配合物与-Re(N∩N)(CO)Cl（其中N∩N = 2,2'-联吡啶或4,4'-二甲基-2,2'-联吡啶）相比的反应活性。我们采用电化学和光谱电化学方法相结合，并结合时间分辨光谱在10个数量级（100皮秒 - 1秒）范围内进行研究，以考察单电子还原的Re(CO)(P∩N)Cl和Re(CO)(As∩N)Cl配合物在质子存在下的特殊反应活性。

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Solvents and Supporting Electrolytes in the Electrocatalytic Reduction of CO.一氧化碳电催化还原中的溶剂与支持电解质
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