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Дата последнего поиска статьи во внешних источниках: 19 декабря 2017 г.
Аннотация:The thermodynamics of chloride dissociation from the 18e arene ruthenium iminophosphonamides [(η6-arene)RuCl{(R′N)2PR2}] (1 a–d) [previously known with arene=C6Me6, R=Ph, R′=p-Tol (a); R=Et, R′=p-Tol (b); R=Ph, R′=Me (c); and new with arene=p-cymene, R=Ph, R′=p-Tol (d)] was assessed in both polar and apolar solvents by variable-temperature UV/Vis, NMR, and 2D EXSY 1H NMR methods, which highlighted the influence of the NPN ligand on the equilibrium parameters. The dissociation enthalpy ΔHd decreases with increasing electron-donating ability of the N- and P-substituents (1 a, 1 d>1 b>1 c) and solvent polarity, and this results in exothermic spontaneous dissociation of 1 c in polar solvents. The coordination of neutral ligands (MeCN, pyridine, CO) to the corresponding 16e complexes [(η6-arene)Ru{(R′N)2PR2}]+PF6− (2 a–d) is reversible; the stability of the 2⋅L adducts depends on the π-accepting ability of L. Carbonylation of 2 a and 2 d resulted in rare examples of cationic arene ruthenium carbonyl complexes (3 a, 3 d), while the monocarbonyl adduct derived from 2 c reacts further with a second equivalent of CO with conversion to carbonyl-carbamoyl complex 3 c, in which one CO molecule is inserted into the Ru−N bond. The new complexes 1 d, 2 d, 3 a, 3 c, and 3 d were isolated and structurally characterized.