Abstract
In this article, we describe a detailed experimental and computational study of the activation mechanism for a highly active PNN-pincer ruthenium(0) pre-catalyst for the hydrogenation of polar organic compounds. The pre-catalyst activates by reaction with two equivalents of hydrogen, resulting in a net oxidative addition to ruthenium and hydrogenation of an imine functional group on the
supporting ligand. The kinetics of pre-catalyst hydrogenation were measured by UV-visible spectroscopy
under catalytically relevant conditions (10-39 bar hydrogen, 298 K). The kinetic data, in combination with density functional theory calculations, support an intriguing autocatalytic mechanism, where the product ruthenium(II) complex catalyzes the hydrogenation of the ruthenium(0) pre-catalyst.
Supplementary materials
Title
Supporting Information
Description
Experimental procedures and alternative mechanistic pathways
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Title
DFT coordinates
Description
Coordinates for DFT structures in XYZ format, viewable in the free program Mercury
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Title
DFT Coordinates for Triplet Structures
Description
DFT Coordinates for Triplet Structures
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Kinetic model and data
Description
Kinetic data, model, and output report files for use in COPASI
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