Room‐Temperature Gas‐Phase CO <sub>2</sub> ‐to‐C <sub>3</sub> Coupling by a 4 <i>f</i> ‐Aromatic Cluster
Abstract
ABSTRACT Room‐temperature conversion of CO 2 into value‐added multi‐carbon products (C 3 or C 3+ species) remains a major challenge due to poor selectivity and limited C−C coupling pathways. Using mass spectrometry, photoelectron imaging spectroscopy, and density functional calculations, we identify the 4 f ‐metalla‐aromatic anion PrB 2 C 2 − , which—despite lacking a C─C bond—exhibits σ and π double aromaticity involving a 4 f atom. We show that PrB 2 C 2 − reacts with CO 2 at room temperature to generate C 3 B 2 O 2 − with a C─C─C backbone. The C 3 ‐chain formation occurs in three stages involving two distinct C−C coupling steps enabled by flexible Pr− X bonding ( X = B, C, O) and Pr‐centered electron shuttling. The unique structure of PrB 2 C 2 − directs CO 2 activation toward C─C─C coupling rather than CO release. These findings deepen the understanding of f ‐block‐mediated small‐molecule activation and provide a new and tailored route for producing products with C─C bonds via CO 2 conversion.
Article Details
Authors (8)
Feng‐Xiang Zhang
Key Laboratory of Cluster Science of Ministry of Education Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials School of Chemistry and Chemical Engineering Beijing Institute of Technology Beijing China
Xiao‐Wang Li
Key Laboratory of Cluster Science of Ministry of Education Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials School of Chemistry and Chemical Engineering Beijing Institute of Technology Beijing China
Ning‐Zheng Li
Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry, Beijing National Laboratory for Molecular Sciences and CAS Research/Education Center of Excellence in Molecular Sciences Chinese Academy of Sciences Beijing China
Sheng‐Gui He
Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry, Beijing National Laboratory for Molecular Sciences and CAS Research/Education Center of Excellence in Molecular Sciences Chinese Academy of Sciences Beijing China
Yu‐Chen Zhang
Center of Basic Molecular Science Department of Chemistry Tsinghua University Beijing China
Li‐Li Xing
Energy and Power Engineering Institute Henan University of Science and Technology Henan China
Donald G. Truhlar
Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute
Jia‐Bi Ma
Key Laboratory of Cluster Science of Ministry of Education Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials School of Chemistry and Chemical Engineering Beijing Institute of Technology Beijing China