Reduction of iron porphyrin chloride complexes of the form (porphyrin)FeCl is known to result in chloride dissociation, with subsequent electron transfer reactions and catalytic formation of H2 when proton sources are present.1 On the other hand (porphyrin)Fe(NO) complexes undergo reversible one-electron reductions2 to form anionic products that can be protonated in the case of picket-fence porphyrins.3 The formation of coordinated HNO ligands3 by this route is of biochemical interest and has been achieved for a very small number of porphyrin model complexes. A related ruthenium compound has been made by an alternate route.4 The reduction chemistry of six-coordinate (por)Ru(NO)X analogues has been previously explored by IR spectroelectrochemistry,5 and depending on the ligand X, apparent NO or X-ligand loss occurs, but in-depth studies in the presence of proton sources have not been published. We report here a systematic study of the consequences of reduction of the title compounds by CV and spectroelectrochemistry. [1] C. Costentin, H. Dridi, J.-M. Saveant J. Am. Chem. Soc. 2014, 136, 13727-13734. [2] Z. Wei, M. D. Ryan Inorg. Chem. 2010, 49, 6948-6954. [3] F. Doctorovich, D.E. Bikiel, J. Pellegrino, S. A. Suárez, M.A. Martí Acc. Chem. Res. 2014, 47, 2907-2916. [4] Lee, J.; Richter-Addo, G. B. J. Inorg. Biochem. 2004, 98, 1247−1250. [5] D. Awasabisah, N. Xu, K. P. Sharma Gautam, D. R. Powell, M. J. Shaw, G. B. Richter-Addo Dalton Trans. 2013, 42, 8537, and references contained therein.

Consequences of reduction of (T(p-X)PP)Ru(NO)Cl (X= H, Cl, Me, OMe)

251st National Meeting (2016)

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