Base hydrolysis of acetonitrile coordinated to a ruthenium(II)_polypyridine complex

On coordination to Ru(terpy)(bipy) 2+ (terpy = 2,2′ : 6′,2″-terpyridine, bipy = 2,2′-bipyridine), acetonitrile is converted to acetamide in aqueous basic solution, through hydroxide attack with a catalytic factor of ca 3 × 10 3 ( k OH = 4.6 × 10 −3 M −1 s −1). This is a remarkable effect for a d 6 t...

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Bibliographic Details
Published in:Polyhedron 1997-01, Vol.16 (11), p.1921-1923
Main Authors: Fagalde, Florencia, Lis de Katz, NoemíD., Katz, Néstor E.
Format: Article
Language:English
Subjects:
acetonitrile complexes
base hydrolysis
catalysis
polypyridine
ruthenium(II)
π-backbonding
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Summary:On coordination to Ru(terpy)(bipy) 2+ (terpy = 2,2′ : 6′,2″-terpyridine, bipy = 2,2′-bipyridine), acetonitrile is converted to acetamide in aqueous basic solution, through hydroxide attack with a catalytic factor of ca 3 × 10 3 ( k OH = 4.6 × 10 −3 M −1 s −1). This is a remarkable effect for a d 6 transition metal in the (II) oxidation state, and can be ascribed to π backbonding from the metal to the polypyridyl ligands, which makes the ruthenium(II) centre more electropositive than ruthenium(II) in the Ru(NH 3) 5 2+ moiety. The final hydrolysis product is the [Ru(terpy)(bipy)(OH)] + complex, since amides, being poor π-acceptor ligands, are rapidly released from the coordination sphere of ruthenium(II).
ISSN:0277-5387
DOI:10.1016/S0277-5387(96)00447-0