A new class of reactive non-metallic chemistry, namely Frustrated Lewis Pair (FLP) is based on a long-range attractive force between two components of Lewis acid and base that are sterically prevented from forming the classical Lewis acid-base adducts. FLP possesses unique property as it undergoes small molecule activation and metal-free catalysis like hydrogenation, CO2 reduction, hydrosilylation, borylation, amination, etc. Owing to its wide applications, FLP has become an emerging science in sustainable catalysis that reduces the dependency on fossil fuels and costly and toxic transition metal. Parallelly, carbodicarbene, a new class of carbon family, bearing two opposite reactive sites (nucleophilic and electrophilic) working simultaneously as a single component can also emulate FLP-like character for catalytic applications.

Prof. Dr. Tiow-Gan Ong at Institute of Chemistry, Academia Sinica and National Taiwan University, previously had led his research team in pioneering advanced techonology for the synthesis of wide variety of carbodicarbene. Recently, Dr. Ong research team consisting of Yi-Chen Chan, Ph.D. student and Dr. Wen-Ching Chen closely collaborated with Professor Hsuan-Ying Chen at Kaohsiung Medical University had employed alcoholic co-modulator to regulate the catalytic activity of carbodicarbene. The synergistic proof-of-concept using carbodicarbene/alcohol system successfully scores unprecedented results in dehydrosilylation, isocyanate cyclotrimerization, L-lactide (LA) and methyl methacrylate (MMA) polymerization.

The experimental efforts were also carried out to understand the enigma of these non-metallic reactions as well as the non-covalent interaction between CDC and BnOH; together with the collaborative computational analysis from Prof. Dr. Lili Zhao offers a pictorial glimpse into road-map and energy profile of this unique reaction. Such a high reactivity in this non-enzymatic catalytic system is attributed to cooperative simple hydrogen bonding and π-π interaction between carbodicarbene and alcohol derivatives.

Several aspects of this work should have broad future impacts on (i) non-metallic organic catalyst and (ii) enrichment and diversification in FLP reactions by adding different “co-modulator” molecules bearing variable functionalities. Immediate translative work is that the carbodicarbene/alcohol system will be applied into the polymerization and co-polymerization process, innovating and building new kind of recycling polymeric materials. At current stage, pilot scale polymerization is under attempt. We are looking forward to form a collaborative alliance with the chemical and material industry for metal-free polymerization in green fashion.

Yi-Chen Chan from Institute of Chemistry, Academia Sinica is the first author of the publication, working closely with team members Dr. Wen-Ching Chen, Professor Dr. Hsuan-Ying Chen, Prof. Dr. Tiow-Gan Ong (also as the principle investigator in charge of this project). The computational analysis with energy profile is solely carried out by Lili Zhao and her team members at Nanjing Tech University. The publication Synergistic Catalysis by Brønsted Acid/Carbodicarbene Mimicking Frustrated Lewis Pair-like Reactivity can be downloaded from Angewandte Chemie website as the attached link below:
https://onlinelibrary.wiley.com/doi/10.1002/anie.202107127
Media Contact:
Dr. Tiow-Gan Ong, Research Fellow/Professor, Institute of Chemistry, Academia Sinica
Email: tgong@gate.sinica.edu.tw
(Tel) +886-2-5572-8648