Benzonitrile Hydrolysis Catalyzed by a Ruthenium(II) Complex

The rate constant for the basic hydrolysis of benzonitrile (PhCN) to benzamide (PhCONH 2 ) in the [Ru II (tpy)(bpy)] moiety (tpy = 2,2' : 6',2"-terpyridine, bpy = 2,2'-bipyridine) (k OH = 3.7 2 10 -2 M -1 s -1 ) is 5 2 10 3 times higher than that of the free ligand and two times...

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Bibliographic Details
Published in:Journal of coordination chemistry 2002, Vol.55 (5), p.587-593
Main Authors: Fagalde, Florencia, de Katz, Noemí Lis, Katz, Néstor
Format: Article
Language:English
Subjects:
Base Hydrolysis
Benzonitrile Complexes
Catalysis
Ruthenium(II)
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Summary:The rate constant for the basic hydrolysis of benzonitrile (PhCN) to benzamide (PhCONH 2 ) in the [Ru II (tpy)(bpy)] moiety (tpy = 2,2' : 6',2"-terpyridine, bpy = 2,2'-bipyridine) (k OH = 3.7 2 10 -2 M -1 s -1 ) is 5 2 10 3 times higher than that of the free ligand and two times higher than that corresponding to the analogous acetonitrile complex. This effect is unusual for a transition metal in the (II) oxidation state, and can be attributed to the π-electron acceptor properties of both the polypyridyl ligands and the phenyl group. Since amides, being poor π-acceptor ligands, are rapidly released from the coordination sphere of ruthenium(II), the final product of this process is the [Ru(tpy)(bpy)(OH)] + complex. The activation parameters for this nitrile hydrolysis have been determined and compare reasonably well with other values for similar reactions.
ISSN:0095-8972
1029-0389
DOI:10.1080/00958970290020892