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Probing N-heterocyclic olefin as ancillary ligand in scandium-mediated \(\hbox {CO}_2\) to CO conversion


The transformation of \(\hbox {CO}_2\) to more reactive and value-added chemical species is a crucial way of reducing environmental impact. The \(\hbox {CO}_{2}\,+ \hbox { M}^{+}\,\rightarrow \hbox { MO}^{+}\,+\) CO reaction, with \({\mathrm{{M}}}=\hbox {transition}\) metal, is an important channel in gas phase, and it has been accomplished by the \(\hbox {Sc}^{+}\) species. Besides being a better choice for sustainable transformations, early transition metals, such as scandium, can open new routes for a variety of novel reactions. In this context, DFT calculations are employed to explore N-heterocyclic olefins (NHOs) molecules as a ligand for scandium complexes in the \(\hbox {CO}_2\) to CO reduction. As revealed by the energetics of the process, the described NHO-Sc systems are able to convert \(\hbox {CO}_2\) to CO in an exoergic way, therefore showing great potential for \(\hbox {CO}_2\) conversion.

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A.P.d.L.B., A.G.S.d.O.F and A.A.C.B thank Grants \(\#\)2017/18238-4, \(\#\)2015/11714-0, \(\#\)2014/25770-6 and \(\#\) 2015/01491-3 from São Paulo Research Foundation (FAPESP), and the support of the High Performance Computing of Universidade de São Paulo (HPC-USP). A.G.S.d.O.F and A.A.C.B also thanks the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) of Brazil for academic support (Grants \(\#\)306830/2018-3, \(\#\)421077/2018-2 and \(\#\)309715/2017-2). This study was also financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance Code 001. The authors also gratefully acknowledge support from FAPESP (Grant No. \(\#\)2017/11631-2), Shell and the strategic importance of the support given by ANP (Brazil’s National Oil, Natural Gas and Biofuels Agency) through the R&D levy regulation.

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de Lima Batista, A.P., de Oliveira-Filho, A.G.S. & Braga, A.A.C. Probing N-heterocyclic olefin as ancillary ligand in scandium-mediated \(\hbox {CO}_2\) to CO conversion. Theor Chem Acc 139, 42 (2020).

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  • \(\hbox {CO}_2\) conversion
  • Early transition metal complexes
  • Scandium
  • NHO ligands
  • DFT