We have recently characterized a mononuclear Ru complex [RuII (damp)(bpy)(H2O)]2+, (damp is 2,6-bis((dimethylamino)methyl)pyridine and bpy is 2,2'-bipyridine; hereafter [RuII-OH2]2+ or 12+ . With a 18O labeling study we unambiguously show that water nucleophilic attack (WNA) is the mechanism employed by the catalyst for O-O bond formation. In addition, a stepwise microscopic mechanistic pathway is proposed on the basis of density functional theory (DFT) calculations, with all intermediate and transition-state structure energetics determined to be consistent with experimental observations. Finally, multireference calculations followed by second order perturbation theory (CASPT2) on compound 12+  and its more highly oxidized analogues are analyzed to describe the character of the Ru-O moiety in the different oxidation states.I will also discuss the performance of some catalysts with formula [M2(trpy)2(bpp)(CH3CO2)]2+ where M=Co, Mn, and Fe for CO2 reduction. We are currently testing them, both experimentally and computationally, in order to discover new pathways for CO2 insertion in the M-H bond. Possible hetero bi-metallic catalysts will also be discussed.  F. Bozoglian, S. Romain, M. Z. Ertem, T. K. Todorova, C. Sens,J. Mola, M. Rodr�guez, I. Romero, J. Benet-Buchholz, X. Fontrodona, C. J. Cramer, L. Gagliardi, A. Llobet, J. Am. Chem. Soc., 2009, 131 , 15176. X. Sala, M. Z. Ertem, L. Vigara, T. K. Todorova, W. Chen, R. C. Rocha, C. J. Cramer, L. Gagliardi, A. Llobet, Angew. Chem. Int. Ed., 2010, 49 , 7745.N. Planas, L. Vigara, C. Cady, P. Miro, P. Huang, L. Hammarstr�m, S. Styring, N. Leidel, H. Dau, M. Haumann,L. Gagliardi, C. J. Cramer, A. Llobet Electronic Structure of Oxidized Complexes Derived from cis-[Ru(II)(bpy)2(H2O)2]2+ and its Photoisomerization Mechanism Inorganic Chemistry, 50(21) , 2011 , pp 11134-11142

Combined experimental and quantum chemical study of catalytic mechanisms for water splitting and CO<sub>2</sub> reduction

244th National Meeting (2012)

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Combined experimental and quantum chemical study of catalytic mechanisms for water splitting and CO2 reduction

Combined experimental and quantum chemical study of catalytic mechanisms for water splitting and CO₂ reduction