Kinetics and mechanisms of homogeneous catalytic reactions. Part 5. Regioselective reduction of heteroaromatic nitrogen compounds catalysed by [OsH(CO)(NCMe)2(PPh3)2]BF4 |
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Authors: | Rosales Merlin Castillo Jéssica González Angel González Larry Molina Karely Navarro Janeth Pacheco Inés Pérez Homero |
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Institution: | (1) Facultad Experimental de Ciencias, Departamento de Química, Laboratorio de Química Inorgánica, Apdo, La Universidad del Zulia (L.U.Z.), 15846 Maracaibo, Venezuela |
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Abstract: | The OsH(CO)(NCMe)2(PPh3)2]BF4 complex (1) is an efficient and regioselective precatalyst for the hydrogenation of the nitrogen-containing ring of quinoline (Q), isoquinoline (iQ), 5,6- and 7,8-benzoquinoline (BQ), and acridine (A) under mild reaction conditions (125 °C and 4 atm H2). Kinetic studies of the hydrogenation of Q and iQ to give tetrahydroquinoline (THQ) and tetrahydroisoquinoline (THiQ), respectively, lead to the rate law r = K
1
k
2/(1 + K
1H2])Os]H2]2, which becomes r = K
1
k
2Os]H2]2, at low hydrogen concentrations (below 1 atm H2); the catalytically active species is of the type OsH(CO)(L)(
1-N)(PPh3)2]BF4 (2a): L = NCMe, N = Q; (2b): L = N = iQ]. The generic mechanisms involve a rapid and partial hydrogenation of the coordinated substrate (N) of complex (2) to yield the corresponding dihydroderivative (DHN) species OsH(CO)(L)(
1-DHN)(PPh3)2]BF4 (3a): L = NCMe, DHN = DHQ; (3b): L = iQ or THiQ, DHN = DHiQ], followed by the rate-determining second hydrogenation of the DHN ligand, which yield OsH(CO)(L)(
1-THN)(PPh3)2]BF4 (4a): L = NCMe, THN = THQ; (4b): L = iQ or THiQ, THN = THiQ]; substitution of the THN ligand by a new molecule of the respective substrate regenerates the active species and restarts the catalytic cycle. For the hydrogenation of acridine to give 9,10-dihidroacridine (acridane), the rate law was r = k
1Os]H2]; the mechanism involves the hydrogenation of the active species OsH(CO)(NCMe)(
1-A)(PPh3)2]BF4
(2c) to yield acridane and the unsaturated species OsH(CO)(NCMe)(PPh3)2]BF4 as the rate-determining step. |
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Keywords: | |
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