title: Redox properties of ruthenium nitrosyl porphyrin complexes with different axial ligation: structural, spectroelectrochemical (IR, UV-visible, and EPR), and theoretical studies.
abstract: Experimental and computational results for different ruthenium nitrosyl porphyrin complexes [(Por)Ru(NO)(X)] ( n+ ) (where Por (2-) = tetraphenylporphyrin dianion (TPP (2 (-) )) or octaethylporphyrin dianion (OEP (2-)) and X = H 2O ( n = 1, 2, 3) or pyridine, 4-cyanopyridine, or 4- N,N-dimethylaminopyridine ( n = 1, 0)) are reported with respect to their electron-transfer behavior. The structure of [(TPP)Ru(NO)(H 2O)]BF 4 is established as an {MNO} species with an almost-linear RuNO arrangement at 178.1(3) degrees . The compound [(Por)Ru(NO)(H 2O)]BF 4 undergoes two reversible one-electron oxidation processes. Spectroelectrochemical measurements (IR, UV-vis-NIR, and EPR) indicate that the first oxidation occurs on the porphyrin ring, as evident from the appearance of diagnostic porphyrin radical-anion vibrational bands (1530 cm (-1) for OEP (*-) and 1290 cm (-1) for TPP (*-)), from the small shift of approximately 20 cm (-1) for nu NO and from the EPR signal at g iso approximately 2.00. The second oxidation, which was found to be electrochemically reversible for the OEP compound, shows a 55 cm (-1) shift in nu NO, suggesting a partially metal-centered process. The compounds [(Por)Ru(NO)(X)]BF 4, where X = pyridines, undergo a reversible one-electron reduction. The site of the reduction was determined by spectroelectrochemical studies to be NO-centered with a ca. -300 cm (-1) shift in nu NO. The EPR response of the NO (*) complexes was essentially unaffected by the variation in the substituted pyridines X. DFT calculations support the interpretation of the experimental results because the HOMO of [(TPP)Ru(NO)(X)] (+), where X = H 2O or pyridines, was calculated to be centered at the porphyrin pi system, whereas the LUMO of [(TPP)Ru(NO)(X)] (+) has about 50% pi*(NO) character. This confirms that the (first) oxidation of [(Por)Ru(NO)(H 2O)] (+) occurs on the porphyrin ring wheras the reduction of [(Por)Ru(NO)(X)] (+) is largely NO-centered with the metal remaining in the low-spin ruthenium(II) state throughout. The 4% pyridine contribution to the LUMO of [(TPP)Ru(NO)(py)] (+) is correlated with the stability of the reduced form as opposed to that of the aqua complex.
authors.affiliation: Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany.
authors.forename: Priti
authors.initials: P
authors.lastname: Singh
authors.forename: Atanu Kumar
authors.initials: AK
authors.lastname: Das
authors.forename: Biprajit
authors.initials: B
authors.lastname: Sarkar
authors.forename: Mark
authors.initials: M
authors.lastname: Niemeyer
authors.forename: Federico
authors.initials: F
authors.lastname: Roncaroli
authors.forename: José A
authors.initials: JA
authors.lastname: Olabe
authors.forename: Jan
authors.initials: J
authors.lastname: Fiedler
authors.forename: Stanislav
authors.initials: S
authors.lastname: Zális
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Kaim
mesh_terms: D018360:Crystallography, X-Ray; D004563:Electrochemistry; D004578:Electron Spin Resonance Spectroscopy; D008024:Ligands; D008665:Metalloporphyrins / Q000737:chemistry*; D009569:Nitric Oxide / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet
chemical_list: D008024:Ligands; D008665:Metalloporphyrins; D009569:Nitric Oxide; D012428:Ruthenium