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Clean and Efficient Transformation of CO2 to Isocyanic Acid: The Important Role of Triatomic Cation ScNH+
journal contribution
posted on 2019-05-14, 00:00 authored by Ming Wang, Chuanxin Sun, Jiatong Cui, Yunhong Zhang, Jiabi MaAchieving
the desired selective transformations of the very stable
CO2 into useful chemicals is quite important for the development
of economically and environmentally sustainable synthetic methods.
Herein, mass spectrometric experiments and quantum-chemical calculations
have identified that ScNH+ reacts quite efficiently with
CO2 under thermal collision conditions to exclusively yield
ScO+ and isocyanic acid (HNCO). This is a novel reaction
type in CO2 activation reactions mediated by gas-phase
ions. In this reaction, the CN double bond has also been formed
for the first time in the gas phase. The mechanism of “migratory
insertion” is proposed. Coupled with the previously reported
reaction of Sc+ with NH3, HNCO can be synthesized
under mild conditions from NH3 and CO2 in quite
simple reactions. The mechanistic information gained in this gas-phase
model reaction can offer fundamental insights relevant to corresponding
processes and further guide on how to design brand new catalysts.