文摘
The complex Rh(acac)(CO)[P(tBu)(CHub>2ub>CH=CHub>2ub>)ub>2ub>] (1) proved to be an efficient precatalyst for the regioselective hydrogenation of quinoline (Q) to 1,2,3,4-tetrahydroquinoline (THQ) under mild reaction conditions (125 °C and 4 atm Hub>2ub>). A kinetic study of this reaction led to the rate law: $$ r \, = \{ K_{1} k_{2} /(1 \, + \, K_{1} {\text{H}}_{ 2} )\} [{\text{Rh}}][{\text{H}}_{ 2} ]^{2} $$which becomes $$ r \, = \, K_{1} k_{2} [{\text{Rh}}][{\text{H}}_{ 2} ]^{2} $$at hydrogen pressures below 4 atm. The active catalytic species is the cationic complex {Rh(Q)ub>2ub>(CO)[P(tBu)(CHub>2ub>CH=CHub>2ub>)ub>2ub>]}+ (2). The mechanism involves the partial hydrogenation of one coordinated Q of (2) to yield a complex containing a 1,2-dihydroquinoline (DHQ) ligand, {Rh(DHQ)(Q)(CO)[P(tBu)(CHub>2ub>CH=CHub>2ub>)ub>2ub>]}+ (3), followed by hydrogenation of the DHQ ligand to give THQ and a coordinatively unsaturated species {Rh(Q)(CO)[P(tBu)(CHub>2ub>CH=CHub>2ub>)ub>2ub>]}+ (4); this reaction is considered to be the rate-determining step. Coordination of a new Q molecule to (4) regenerates the active species (2) and restarts the catalytic cycle. 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Laboratorio de Química Inorgánica, Departamento de Química, Facultad Experimental de Ciencias, Universidad del Zulia (L.U.Z.), Apdo. 526, Maracaibo, Venezuela 2. Centro de Química, Instituto Venezolano de Investigaciones Científicas (I.V.I.C.), Apdo. 21827, Caracas, 1020, Venezuela Continue reading... To view the rest of this content please follow the download PDF link above.