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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Pentamethylcyclopentadienyl Half-Sandwich Diazoalkane Complexes of Ruthenium: Preparation and Reactivity
Gabriele Albertin1, Stefano Antoniutti1, Marco Bortoluzzi1
1Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia , Via Torino 155, 30172 Mestre Venezia, Italy.
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).
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