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Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
A computational study of O-O bond formation catalyzed by mono- and bis-MnIV-corrole complexes
Timofei Privalov1, Licheng Sun, Björn Akermark
1Organic Chemistry, KTH Chemical Science and Engineering, 10044 Stockholm, Sweden. priti@kth.se
Abstract:
A detailed computational study of O-O bond formation, catalyzed by monomeric and dimeric Mn-corrole complexes, is reported. The model explicitly takes into account the solvent, with respect to the first and second coordination spheres, while the bulk solvent is described by the polarizable continuum model. Two reaction mechanisms are proposed and computationally characterized: the concerted and the two-step mechanisms. The concerted mechanism is based on a OH--MnIVO interaction via the outer-sphere pathway involving the bridging solvent molecules in the first coordinating sphere. The two-step mechanism is proposed to operate via the coordination of a hydroxide to the MnIV ion, forming a MnO(OH)--corrole complex with a strongly nonplanar corrole ligand. Comparison of the proposed mechanisms with available experimental data is performed.
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