title: Pentamethylcyclopentadienyl Half-Sandwich Diazoalkane Complexes of Ruthenium: Preparation and Reactivity.
abstract: The diazoalkane complexes [Ru(η(5)-C5Me5)(N2CAr1Ar2){P(OR)3}L]BPh4 (1-4) [R = Me, L = P(OMe)3 (1); R = Et, L = P(OEt)3 (2); R = Me, L = PPh3 (3); R = Et, L = PPh3 (4); Ar1 = Ar2 = Ph (a); Ar1 = Ph, Ar2 = p-tolyl (b); Ar1Ar2 = C12H8 (c); Ar1 = Ph, Ar2 = PhC(O) (d)] and [Ru(η(5)-C5Me5){N2C(C12H8)}{PPh(OEt)2}(PPh3)]BPh4 (5c) were prepared by allowing chloro-compounds RuCl(η(5)-C5Me5)[P(OR)3]L to react with the diazoalkane Ar1Ar2CN2 in the presence of NaBPh4. Treatment of complexes 1-4 with H2O afforded 1,2-diazene derivatives [Ru(η(5)-C5Me5)(η(2)-NH═NH){P(OR)3}L]BPh4 (6-9) and ketone Ar1Ar2CO. A reaction path involving nucleophilic attack by H2O on the coordinated diazoalkane is proposed and supported by density functional theory calculations. The complexes were characterized spectroscopically (IR and (1)H, (31)P, (13)C, (15)N NMR) and by X-ray crystal structure determination of [Ru(η(5)-C5Me5)(N2CC12H8){P(OEt)3}2]BPh4 (2c) and [Ru(η(5)-C5Me5)(η(2)-NH═NH){P(OEt)3}2]BPh4 (7).
authors.affiliation: Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia , Via Torino 155, 30172 Mestre Venezia, Italy.
authors.forename: Gabriele
authors.initials: G
authors.lastname: Albertin
authors.affiliation: Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia , Via Torino 155, 30172 Mestre Venezia, Italy.
authors.forename: Stefano
authors.initials: S
authors.lastname: Antoniutti
authors.affiliation: Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia , Via Torino 155, 30172 Mestre Venezia, Italy.
authors.forename: Marco
authors.initials: M
authors.lastname: Bortoluzzi
authors.affiliation: Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia , Via Torino 155, 30172 Mestre Venezia, Italy.
authors.forename: Alessandra
authors.initials: A
authors.lastname: Botter
authors.affiliation: Departamento de Química Inorgánica, Facultade de Química, Edificio de Ciencias Experimentais, Universidade de Vigo , 36310 Vigo (Galicia), Spain.
authors.forename: Jesús
authors.initials: J
authors.lastname: Castro