Catalytic transfer hydrogenation with terdentate CNN ruthenium complexes: The influence of the base

The catalytic activity of the terdentate complex [RuCl(CNN)(dppb)] (A) [dppb=Ph2P(CH2)(4)PPh2; HCNN = 6-(4 '-methylphenyl)-2-pyridyl-methylamine] in the transfer hydrogenation of acetophenone (S) with 2-propanol has been found to be dependent on the base concentration. The limit rate has been observed when NaOiPr is used in high excess (A/base molar ratio > 10). The amino-isopropoxide species [Ru(OiPr)(CNN)(dppb)] (B), which forms by reaction of A with sodium isopropoxide via displacement of the chloride, is catalytically active. The rate of conversion of acetophenone obeys second-order kinetics v= k[S][B] with the rate constants in the range 218 8 (40 degrees C) to 3000 70 M(-1)s(-1) (80 C). The activation parameters, evaluated from the Eyring equation are Delta H-not equal =14.0 +/- 0.2 kcal mol(-1) and Delta S-not equal = -3.2 +/- 0.5 eu. In a pre-equilibrium reaction with 2-propanol complex B gives the cationic species [Ru(CNN)(dppb)(HOiPr)](+) [OiPr](-) (C) with K 2 x 10(-5) M. The hydride species [RuH(CNN)(dppb)] (H), which forms from B via (beta-hydrogen elimination process, catalyzes the reduction of S and, importantly, its activity increases by addition of base. The catalytic behavior of the hydride H has been compared to that of the system A/NaOiPr (1:1 molar ratio) and indicates that the two systems are equivalent.