Carbon Dioxide Hydrogenation to Formate Catalyzed by a Bench-Stable, Non-Pincer-Type Mn(I) Alkylcarbonyl Complex

Sylwia Kostera; Stefan Weber; Maurizio Peruzzini; Luis F Veiros; Karl Kirchner; Luca Gonsalvi

doi:10.1021/acs.organomet.0c00710

Carbon Dioxide Hydrogenation to Formate Catalyzed by a Bench-Stable, Non-Pincer-Type Mn(I) Alkylcarbonyl Complex

Organometallics. 2021 May 10;40(9):1213-1220. doi: 10.1021/acs.organomet.0c00710. Epub 2021 Apr 20.

Authors

Sylwia Kostera¹, Stefan Weber², Maurizio Peruzzini¹, Luis F Veiros³, Karl Kirchner², Luca Gonsalvi¹

Affiliations

¹ Consiglio Nazionale delle Ricerche (CNR), Istituto di Chimica dei Composti Organometallici (ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino (Firenze), Italy.
² Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163-AC, A-1060 Vienna, Austria.
³ Centro de Química Estrutural and Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av Rovisco Pais, 1049-001 Lisboa, Portugal.

Abstract

The catalytic reduction of carbon dioxide is a process of growing interest for the use of this simple and abundant molecule as a renewable building block in C1-chemical synthesis and for hydrogen storage. The well-defined, bench-stable alkylcarbonyl Mn(I) bis(phosphine) complex fac-[Mn(CH₂CH₂CH₃)(dippe)(CO)₃] [dippe = 1,2-bis(diisopropylphosphino)ethane] was tested as an efficient and selective non-precious-metal precatalyst for the hydrogenation of CO₂ to formate under mild conditions (75 bar total pressure, 80 °C), in the presence of a Lewis acid co-catalyst (LiOTf) and a base (DBU). Mechanistic insight into the catalytic reaction is provided by means of density functional theory (DFT) calculations.