Cationic ruthenium(II) systems. Part 1. The preparation and reactivity of diene(hydrazine)ruthenium(II) cations, and the formation of aminobonded hydrazone complexes
- 1 January 1977
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 19,p. 1809-1815
- https://doi.org/10.1039/dt9770001809
Abstract
The polymeric species [{RuCl2(diene)}n](1; n > 2) and the appropriate hydrazine have been used to prepare the salts [Ru(diene)(N2H4)4][BPh4]2{2; diene = bicyclo[2.2.1]hepta-2,5-diene(nbd) or cyclo-octa-1,5-diene(cod)}[Ru(cod)(NH2NHMe)4][PF6]2, and [RuH(cod)(NH2NRR′)3]X [R = R′= Me, X = BPh4(3) or X = PF6(4); R = H, R′= H or Me, X = BPh4(5)]. Solutions of (2; diene = cod) in refluxing acetone–ethanol mixtures give a complex of stoicheiometry [Ru(BPh4)(cod)](6) and, in the presence of ligands L, [Ru(cod)L4][BPh4]2[L = pyridine (py), Me2SO (dmso), or MeCN], [RuL6][BPh4]2(L = 4Me-py or dmso), and the hydrazone-containinig salts [Ru(NH2NCMe2)2L4]2{7; L = P(OMe)3, P(OEt)3, P[(OCH2)3CR](R = Me or Et), and PPh(OMe)2}. Treatment of [Ru(cod)(NH2NHMe)4][PF6]2 with PPh(OMe)2 in acetone produces [Ru(NH2NHMe)2{PPh(OMe)2}4]-[PF6]2. Substitution reactions of (3) give [RuH(cod)L3]+[L = py, 4Me-py, or MeCN] and [RuHL5]+[L = PPh(OMe)2, P(OEt)3, or PPh(OEt)2], while the neutral complexes [{RuXH(cod)}2NH2NMe2](8) have been prepared from (3) and LiX (X = Cl or Br) in methanol or acetone solutions. Complex (8) may be converted into [RuXH(PPh3)3] and [RuXH(cod)(PMePh2)2](X = Cl or Br) with PPh3 and PMePh2 respectively.Keywords
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