Previous experimental work has demonstrated the ability to promote small molecule activation using silyl/bis(phosphine) rhodium pincer complexes. We have used density functional theory (DFT) to investigate the mechanisms of catalytic alkene hydrogenation and the reductive cleavage of carbon dioxide driven by this class of complexes, with an eye toward identifying rhodium/silicon cooperation. For hydrogenation, computational results suggest competition between unimolecular and bimolecular pathways for alkane release with no Rh/Si cooperation, consistent with experimental findings. In contrast, intimate involvement of silicon is implicated in the activation of carbon dioxide, which proceeds via a [2+2] cycloaddition to a transient rhodium silylene, yielding a siloxide carbonyl complex. The full mechanism of this reaction is the subject of ongoing computational and experimental studies.<br/>

Computational studies of rhodium-catalyzed hydrogenation and carbon dioxide activation

253rd National Meeting (2017)

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