Highly Active, Low-Valence Molybdenum- and Tungsten-Amide Catalysts for Bifunctional Imine-Hydrogenation Reactions

The reactions of [M(NO)(CO)(4)(ClAlCl3)] (M=Mo, W) with (iPr(2)PCH(2)CH(2))(2)NH, ((PNP)-P-H) at 90 degrees C afforded [M(NO)(CO)((PNP)-P-H)Cl] complexes (M=Mo, 1a; W, 1b). The treatment of compound 1a with KOtBu as a base at room temperature yielded the alkoxide complex [Mo(NO)(CO)((PNP)-P-H)(OtBu)] (2a). In contrast, with the amide base Na[N(SiMe3)(2)], the (PNP)-P-H ligand moieties in compounds 1a and 1b could be deprotonated at room temperature, thereby inducing dehydrochlorination into amido complexes [M(NO)(CO)(PNP)] (M=Mo, 3a; W, 3b; PNP=(iPr(2)PCH(2)CH(2))(2)N)). Compounds 3a and 3b have pseudo-trigonal-bipyramidal geometries, in which the amido nitrogen atom is in the equatorial plane. At room temperature, compounds 3a and 3b were capable of adding dihydrogen, with heterolytic splitting, thereby forming pairs of isomeric amine-hydride complexes [Mo(NO)(CO)H((PNP)-P-H)] (4a(cis) and 4a(trans)) and [W(NO)(CO)H((PNP)-P-H)] (4b(cis) and 4b(trans); cis and trans correspond to the position of the H and NO groups). H-2 approaches the Mo/WN bond in compounds 3a,b from either the CO-ligand side or from the NO-ligand side. Compounds 4a(cis) and 4a(trans) were only found to be stable under a H-2 atmosphere and could not be isolated. At 140 degrees C and 60bar H-2, compounds 3a and 3b catalyzed the hydrogenation of imines, thereby showing maximum turnover frequencies (TOFs) of 2912 and 1120h(-1), respectively, for the hydrogenation of N-(4-methoxybenzylidene)aniline. A Hammett plot for various para-substituted imines revealed linear correlations with a negative slope of -3.69 for para substitution on the benzylidene side and a positive slope of 0.68 for para substitution on the aniline side. Kinetics analysis revealed the initial rate of the hydrogenation reactions to be first order in c(cat.) and zeroth order in c(imine). Deuterium kinetic isotope effect (DKIE) experiments furnished a low k(H)/k(D) value (1.28), which supported a Noyori-type metal-ligand bifunctional mechanism with H-2 addition as the rate-limiting step.