Pincer ligated coordination complexes of base metals have shown remarkable catalytic activity for hydrogenation/dehydrogenation of CO2. The recently reported MeNCH2CH2(Pr-i(2))Co(I)PNP-pincer complex was shown to exhibit substantially higher catalytic activity in comparison to the corresponding catalyst, HNCH2CH2(Pr-i(2))Co(I)PNP, bearing a secondary nitrogen center on the pincer ligand. Here, we computationally investigate the mechanisms for hydrogenation of CO2 to formate catalyzed by these two Co-PNP complexes to explain how such a small structural difference could have a sizable impact on their catalytic activity. Plausible hydrogenation routes were examined in details and our findings provide solid support for the experimental observations. Our results reveal that such trends in catalytic activity could be explained from the lower activation barrier for the hydride transfer step upon changing the pincer nitrogen center from secondary to tertiary.