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An in-depth theoretical study has been performed to investigate the mechanism of dehydrogenative silylation catalyzed by the aryl-substituted bis(imino)pyridine cobalt(Ⅰ ) methyl complex,(MesPDI)CoPH3(MesPDI=2,6-(2,4,6-Me3C6H2-N=CMe)2C5H3N).