2 research outputs found
Heteroditopic Chelating NHC Ligand-Supported Co<sup>III</sup> Complexes: Catalysts for the Reductive Functionalization of Carbon Dioxide under Ambient Conditions
Synthesis and characterization of heteroditopic chelating
NHC ligand-supported
air stable CoIII–NHC complexes (1a–d), featuring variable triazole N-substituents and thus, being
structurally tunable, are reported. These complexes were observed
to be very effective catalysts for the reductive functionalization
of CO2 with aromatic amines using hydrosilane under ambient
conditions (1 bar of CO2 pressure and room temperature)
to yield diverse N-formylated amines, and importantly, the catalytic
activity of the complexes was found to be reasonably tuned by the
triazole N-substituents, which is probably due to some electronic
modulations, supported by electrochemical analysis, rather than any
considerable steric alterations as indicated by the percent buried
volume calculation. Notably, the corresponding CoIII–NHC
complexes generated in situ were also found to be
equally effective. It is worth mentioning that this is the first report
on the effective N-formylation of less nucleophilic aromatic primary
amines by employing a homogeneous Co complex, to the best of our knowledge.
In addition, control experiments suggest that this protocol proceeds
via Co hydride and formoxysilane intermediate formation
Heteroditopic Chelating NHC Ligand-Supported Co<sup>III</sup> Complexes: Catalysts for the Reductive Functionalization of Carbon Dioxide under Ambient Conditions
Synthesis and characterization of heteroditopic chelating
NHC ligand-supported
air stable CoIII–NHC complexes (1a–d), featuring variable triazole N-substituents and thus, being
structurally tunable, are reported. These complexes were observed
to be very effective catalysts for the reductive functionalization
of CO2 with aromatic amines using hydrosilane under ambient
conditions (1 bar of CO2 pressure and room temperature)
to yield diverse N-formylated amines, and importantly, the catalytic
activity of the complexes was found to be reasonably tuned by the
triazole N-substituents, which is probably due to some electronic
modulations, supported by electrochemical analysis, rather than any
considerable steric alterations as indicated by the percent buried
volume calculation. Notably, the corresponding CoIII–NHC
complexes generated in situ were also found to be
equally effective. It is worth mentioning that this is the first report
on the effective N-formylation of less nucleophilic aromatic primary
amines by employing a homogeneous Co complex, to the best of our knowledge.
In addition, control experiments suggest that this protocol proceeds
via Co hydride and formoxysilane intermediate formation