Room-Temperature Gas-Phase CO₂-to-C₃ Coupling by a 4f-Aromatic Cluster

TY - JOUR

T1 - Room-Temperature Gas-Phase CO2-to-C3 Coupling by a 4f-Aromatic Cluster

AU - Zhang, Feng Xiang

AU - Li, Xiao Wang

AU - Li, Ning Zheng

AU - He, Sheng Gui

AU - Zhang, Yu Chen

AU - Xing, Li Li

AU - Truhlar, Donald G.

AU - Ma, Jia Bi

N1 - Publisher Copyright: © 2026 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.

PY - 2026/5/25

Y1 - 2026/5/25

N2 - Room-temperature conversion of CO2 into value-added multi-carbon products (C3 or C3+ 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 4f-metalla-aromatic anion PrB2C2−, which—despite lacking a C─C bond—exhibits σ and π double aromaticity involving a 4f atom. We show that PrB2C2− reacts with CO2 at room temperature to generate C3B2O2− with a C─C─C backbone. The C3-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 PrB2C2− directs CO2 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 CO2 conversion.

AB - Room-temperature conversion of CO2 into value-added multi-carbon products (C3 or C3+ 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 4f-metalla-aromatic anion PrB2C2−, which—despite lacking a C─C bond—exhibits σ and π double aromaticity involving a 4f atom. We show that PrB2C2− reacts with CO2 at room temperature to generate C3B2O2− with a C─C─C backbone. The C3-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 PrB2C2− directs CO2 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 CO2 conversion.

KW - CO conversion

KW - Pr─C bond

KW - aromaticity

KW - praseodymium

KW - rare-earth

UR - https://www.scopus.com/pages/publications/105035705224

U2 - 10.1002/anie.6756333

DO - 10.1002/anie.6756333

M3 - Article

AN - SCOPUS:105035705224

SN - 1433-7851

VL - 65

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 22

M1 - e6756333

ER -