Benzonitrile Hydrolysis Catalyzed by a Ruthenium(II) Complex

Author： Fagalde Florencia Lis de Katz Noemí Katz Néstor

ISSN： 0095-8972

Source： Journal of Coordination Chemistry, Vol.55, Iss.5, 2002-01, pp. : 587-593

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Abstract

The rate constant for the basic hydrolysis of benzonitrile (PhCN) to benzamide (PhCONH₂) in the [Ru^II(tpy)(bpy)] moiety (tpy = 2,2′ : 6′,2″-terpyridine, bpy = 2,2′-bipyridine) (k_OH = 3.7 × 10⁻² M⁻¹s⁻¹) is 5 × 10³ 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.