10.1021/acs.jpca.9b02133.s001
Ming Wang
Ming
Wang
Chuanxin Sun
Chuanxin
Sun
Jiatong Cui
Jiatong
Cui
Yunhong Zhang
Yunhong
Zhang
Jiabi Ma
Jiabi
Ma
Clean and Efficient Transformation of CO<sub>2</sub> to Isocyanic Acid: The Important
Role of Triatomic Cation ScNH<sup>+</sup>
American Chemical Society
2019
novel reaction type
gas-phase model reaction
CO 2 activation reactions
Triatomic Cation ScNH
CO 2
NH 3
HNCO
2019-05-14 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Clean_and_Efficient_Transformation_of_CO_sub_2_sub_to_Isocyanic_Acid_The_Important_Role_of_Triatomic_Cation_ScNH_sup_sup_/8204156
Achieving
the desired selective transformations of the very stable
CO<sub>2</sub> 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<sup>+</sup> reacts quite efficiently with
CO<sub>2</sub> under thermal collision conditions to exclusively yield
ScO<sup>+</sup> and isocyanic acid (HNCO). This is a novel reaction
type in CO<sub>2</sub> 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<sup>+</sup> with NH<sub>3</sub>, HNCO can be synthesized
under mild conditions from NH<sub>3</sub> and CO<sub>2</sub> 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.