Electrocatalytic reduction of carbon dioxide with a manganese(I)tricarbonyl complex containing a nonaromatic α‑diimine ligand

Zeng, Q., Tory, J. and Hartl, F. ORCID: https://orcid.org/0000-0002-7013-5360 (2014) Electrocatalytic reduction of carbon dioxide with a manganese(I)tricarbonyl complex containing a nonaromatic α‑diimine ligand. Organometallics, 33 (18). pp. 5002-5008. ISSN 1520-6041 doi: 10.1021/om500389y

Abstract/Summary

The 2e reduced anion [Mn(CO)3(iPr-DAB)]− (DAB = 1,4- diazabuta-1,3-diene, iPr = isopropyl) was shown to convert in the presence of CO2 and a small amount of water to the unstable complex [Mn(CO)3(iPr-DAB)(η1-OCO2H)] (OCO2H− = unidentate bicarbonate) that was further reductively transformed to give a stable catalytic intermediate denoted as X2, showing νs(OCO) 1672 and 1646 (sh) cm−1. The subsequent cathodic shift by ca. 650 mV in comparison to the single 2e cathodic wave of the parent [Mn(CO)3(iPr-DAB)Br] triggers the reduction of intermediate X2 and catalytic activity converting CO2 to CO. Infrared spectroelectrochemistry has revealed that the high excess of CO generated at the cathode leads to the conversion of [Mn(CO)3(iPr-DAB)]− to inactive [Mn(CO)5]−. In contrast, the five-coordinate anion [Mn(CO)3(pTol-DAB)]−(pTol = 4-tolyl) is completely inert toward both CO2 and H2O (solvolysis). This detailed spectroelectrochemical study is a further contribution to the development of sustainable electro- and photoelectrocatalysts of CO2 reduction based on abundant first-row transition metals, in particular manganese.

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/37854
Item Type	Article
Refereed	Yes
Divisions	Interdisciplinary centres and themes > Chemical Analysis Facility (CAF) Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Publisher	American Chemical Society
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