A New Member of the Growing Family of Interconvertible {RuNO} Species. Redox and Acid-Base Characterization of [Ru((CHpy)Me[9]aneN)(NO)]
European Journal of Inorganic Chemistry, ISSN: 1099-0682, Vol: 2021, Issue: 46, Page: 4842-4855
2021
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Example: if you select the 1-year option for an article published in 2019 and a metric category shows 90%, that means that the article or review is performing better than 90% of the other articles/reviews published in that journal in 2019. If you select the 3-year option for the same article published in 2019 and the metric category shows 90%, that means that the article or review is performing better than 90% of the other articles/reviews published in that journal in 2019, 2018 and 2017.
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Article Description
The preparation and characterization of a new ruthenium nitrosyl based on the pentadentate ligand (CHpy)Me[9]aneN (1-methyl-4,7-bis(pyridin-2-ylmethyl)-1,4,7-triazacyclononane) is reported. The octahedral species contains a {RuNO} fragment and can be isolated in the solid state as a PF salt. In acetonitrile, this platform allows exploring the reduction processes in 1-electron steps from {RuNO} to {RuNO}, with associated E° values of 0.421 V and −0.628 V (vs. Ag/AgCl, 3 M NaCl), respectively. The {RuNO} species is paramagnetic, its EPR spectrum in vitrified acetonitrile at 90 K is consistent with an S= (Formula presented.) center with g=(2.0095, 1.9992, 1.8785) coupled to a N nucleus, with A=(6.9, 30.24, 1.85)×10 cm. In acidified aqueous solution, the first reduction process at 0.101 V leads to the formation of {RuNO}, as in aprotic medium (acetonitrile). However, the incorporation of a second electron is coupled to a protonation process of the nitroxyl group, generating a coordinated azanone (HNO) compound with pK(HNO)=11.0. Spectroscopic information obtained via spectroelectrochemistry and electronic structure calculations assist in the rationalization of results. Overall, this new compound enhances the library of nitrosylated Ru species with combined redox, acid-base, and spectroscopic characterization in water and confirms experimental correlations found in related species.
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