title: Hydrolysis of coordinated diazoalkanes to yield side-on 1,2-diazene derivatives.
abstract: Diazoalkane complexes [Ru(η(5)-C5Me5)(N2CAr1Ar2)(PPh3){P(OR)3}]BPh4 [R = Me (1), Et (2); Ar1 = Ar2 = Ph (a); Ar1 = Ph, Ar2 = p-tolyl (b); Ar1Ar2 = C12H8 (c)] were prepared by allowing chloro complexes RuCl(η(5)-C5Me5)(PPh3)[P(OR)3] to react with diazoalkane Ar1Ar2CN2 in ethanol. The treatment of compounds 1 and 2 with H2O afforded 1,2-diazene derivatives [Ru(η(5)-C5Me5)(η(2)-NH═NH)(PPh3){P(OR)3}]BPh4 (3 and 4) and ketone Ar1Ar2CO. A reaction path involving nucleophilic attack by H2O on the coordinated diazoalkane is proposed. The complexes were characterized spectroscopically (IR and NMR) and by X-ray crystal structure determination of [Ru(η(5)-C5Me5)(η(2)-NH═NH)(PPh3){P(OMe)3}]BPh4 (3).
authors.affiliation: Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia , Dorsoduro 2137, 30123 Venezia, Italy.
authors.forename: Gabriele
authors.initials: G
authors.lastname: Albertin
authors.forename: Stefano
authors.initials: S
authors.lastname: Antoniutti
authors.forename: Alessandra
authors.initials: A
authors.lastname: Botter
authors.forename: Jesús
authors.initials: J
authors.lastname: Castro