Electrochemical properties and C–H bond oxidation activity of [Ru(tpy)(pyalk)Cl]+ and [Ru(tpy)(pyalk)(OH)]+. Issue 29 (6th July 2018)

• Record Type: Journal Article
• Authors: Nilles, Christian K.; Herath, Hashini N. K.; Fanous, Hanna; Ugrinov, Angel; Parent, Alexander R.
• Is Part Of: Dalton transactions. Volume 47:Issue 29(2018)
• Page Start: 9701
• Page End: 9708
• Publication Date: 2018-07-06
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt02260g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : An O-donor ligand leads to low Ru(ii /iii ) potentials. Abstract : [Ru(tpy)(pyalk)Cl]Cl (pyalk = 2-(2′-pyridyl)-2-propanol) was synthesized and characterized crystallographically and electrochemically. Upon dissolution in water and acetonitrile, [Ru(tpy)(pyalk)Cl]Cl was found to form [Ru(tpy)(pyalk)Cl] + and [Ru(tpy)(pyalk)(OH)] +, respectively. The Ru(ii /iii ) couple of [Ru(tpy)(pyalk)Cl] + was found to be relatively low compared to that of other Ru complexes in acetonitrile, but the Ru(iii /iv ) couple was not significantly different than other Ru complexes bearing anionic ligands. Pourbaix diagrams were generated for [Ru(tpy)(phpy)(OH2 )] + (phpy = 2-phenylpyridine) and [Ru(tpy)(pyalk)(OH)] + in water, and it was found that [Ru(tpy)(pyalk)(OH)] + has a lower Ru(ii /iii ) potential than [Ru(tpy)(phpy)(OH2 )] + under neutral to alkaline pH. [Ru(tpy)(pyalk)(OH)] + was found to catalyze C–H bond hydroxylation of secondary alkanes and epoxidation of alkenes using cerium(iv ) ammonium nitrate as the primary oxidant.