Synthetic Route of 37366-09-9. Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer
Four half-sandwich ruthenium(II) complexes [(eta6-C6H6)Ru(L1-O)][PF6] (1), [(eta6-C6H6)Ru(L2-O)][PF6] (2), [(eta6-C6H6)Ru(L3-O)][PF6] (3), [(eta6-C6H6)Ru(L4-O)][PF6] (4a), and [(eta6-C6H6)Ru(L4-O)][BPh4] (4b) [L1-OH, 4-nitro-6-{[(2?-(pyridin-2-yl)ethyl)methylamino]methyl}-phenol; L2-OH, 2,4-di-tert-butyl-6-{[(2?-(pyridin-2-yl)ethyl)methylamino]methyl}-phenol; L3-OH, 2,4-di-tert-butyl-6-{[2?-((pyridin-2-yl)benzylamino)methyl}-phenol; L4-OH, 2,4-di-tert-butyl-6-{[(2?-imethylaminoethyl)methylamino]methyl}-phenol (L4-OH)], supported by a systematically varied series of tridentate phenolate-based pyridylalkylamine and alkylamine ligands are reported. The molecular structures of 1-3, 4a, and 4b have been elucidated in solution using 1H NMR spectroscopy and of 1, 3, and 4b in the solid state by X-ray crystallography. Notably, due to coordination by the ligands the Ru center assumes a chiral center and in turn the central amine nitrogen also becomes chiral. The 1H NMR spectra exhibit only one set of signals, suggesting that the reaction is completely diastereoselective [1: SRu,SN/RRu,RN; 2: RRu,RN/SRu,SN; 3: SRu,RN/RRu,SN; 4b: SRu,RN/RRu,SN]. The crystal packing in 1 and 3 is stabilized by C-H…O interactions, in 4b no meaningful secondary interactions are observed. From the standpoint of generating phenoxyl radical, as investigated by cyclic voltammetry (CV), complex 1 is redox-inactive in MeCN solution. However, 2, 3, and 4a generate a one-electron oxidized phenoxyl radical coordinated species [2]2+{radical dot}, [3]2+{radical dot}, and [4a]2+{radical dot}, respectively. The radical species are characterized by CV, UV-Vis, and EPR spectroscopy. The stability of the radical species has been determined by measuring the decay constant (UV-Vis spectroscopy).
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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI