Coordinatively Labile 18-Electron Arene Ruthenium Iminophosphonamide Complexes.

The thermodynamics of chloride dissociation from the 18e arene ruthenium iminophosphonamides [(η6 -arene)RuCl{(R'N)2 PR2 }] (1 a-d) [previously known with arene=C6 Me6 , 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 1 H 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)2 PR2 }]+ 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.