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Issue 22, 1997
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Preparation of mono- and bis-(hydrazine) complexes of ruthenium(II)


Hydrazine complexes [RuH(R1NHNH2)L4]BPh4 1–3, [Ru(R1NHNH2)2L4][BPh4]2 4–6 [R1 = H, Me, Ph, 4-MeC6H4 or 4-O2NC6H4; L = P(OEt)3, PPh(OEt)2 or P(OMe)3] were prepared by allowing the hydride species [RuH2L4] to react, first with triflic acid (CF3SO3H) and then with an excess of the appropriate hydrazine. The derivatives [RuH(Me2NNH2){P(OEt)3}4]BPh4 1f, [Ru(η1-OSO2CF3)(Me2NNH2){P(OEt)3}4]BPh4 9 and [Ru(η2-Ph-CONHNH2)L4][BPh4]2 7,8 [L = P(OEt)3 or PPh(OEt)2] were also obtained. The formulation and geometry in solution of the compounds were established by infrared and 1H and 31P NMR spectroscopy. The reaction of the bis(nitrile) complexes [Ru(R2CN)2L4][BPh4]2 [R2 = Me or MeC6H4; L = P(OEt)3 or PPh(OEt)2] with hydrazines depends not only on the experimental conditions, but also on the nature of the phosphite and the hydrazine used. Thus, nitrilehydrazine [Ru(R1NHNH2)(R2CN)L4][BPh4]2 10–13 [L = P(OEt)3 or PPh(OEt)2] or amidrazone derivatives [Ru{η2-NH[double bond, length half m-dash]C(R2)N(R1)NH2}{P(OEt)3}4][BPh4]2 14,15 (R1 = H or Me) were obtained together with the bis(hydrazine) compounds [Ru(R1NHNH2)2L4][BPh4]2. Reaction of the arylhydrazine complexes 1–6 and 10–13 with Pb(O2CMe)4 at –30 °C in CH2Cl2 resulted in selective oxidation of the arylhydrazine ligand giving the aryldiazene derivatives [RuH(R1N[double bond, length half m-dash]NH)L4]BPh4, [Ru(R1N[double bond, length half m-dash]NH)2L4][BPh4]2 and [Ru(R1N[double bond, length half m-dash]NH)(R2CN)L4][BPh4]2 (R1 = Ph, 4-MeC6H4 or 4-O2NC6H4). Treatment of hydrazine NH2NH2 and methylhydrazine MeNHNH2 complexes 1–6 with Pb(O2CMe)4, instead, afforded the acetate [Ru(η2-O2CMe)L4]BPh4 derivatives which were characterised by a crystal structure determination of [Ru(η2-O2CMe){P(OEt)3}4]BPh4. The co-ordination of ruthenium is distorted octahedral with approximate C 2v symmetry and the acetate is bidentate.

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Article information

J. Chem. Soc., Dalton Trans., 1997, 4435-4444
Article type

Preparation of mono- and bis-(hydrazine) complexes of ruthenium(II)

G. Albertin, S. Antoniutti, A. Bacchi, E. Bordignon, P. Matteo Dolcetti, S. A. A. B. E. B. P. M. D. G. ,. P. and S. A. A. B. E. B. P. M. D. G. ,. P., J. Chem. Soc., Dalton Trans., 1997, 4435
DOI: 10.1039/A702712E

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