Synthesis and rearrangement reactions of dihalogenotris- and dihalogenotetrakis-(tertiary phosphine)ruthenium(II) compounds
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 16-17,p. 1663-1672
- https://doi.org/10.1039/dt9750001663
Abstract
The reactions of [RuCl2(PPh3)4] with several tertiary phosphine ligands in various solvents have been examined. Whereas prolonged reaction in ethanol or dichloromethane leads to the well known ionic dimers [Ru2Cl3L6]Cl(L = PEtPh2, PEt2Ph, or PMe2Ph), reaction in non-polar solvents such as hexane or light petroleum (b.p. 60–80 °C) produces neutral complexes. For L = PEtPh2, [RuCl2(PEtPh2)3] has been isolated although this readily converts to the triple chloride-bridged dimer [(Ph2EtP)3RuCl3RuCl(PEtPh2)2] in non-polar and [Ru2Cl3(PEtPh2)3]Cl in polar media. For L = PEt2Ph and PClPh2, only [L3RuCl3RuClL2] can be isolated although 31P n.m.r. studies indicate the presence of [RuCl2(PEt2Ph)3] in the reaction mixture. For L = PMe2Ph, cis-[RuCl22(PMe2Ph)4] is formed although this very readily rearranges to [Ru2Cl3(PMe2Ph)6]Cl. Preliminary studies indicate that similar compounds are formed from [RuBr2(PPh3)4]. All these compounds {including [RuCl2(PPh3)3 and 4]} have been extensively studied by variable-temperature 31P n.m.r. spectroscopy and an overall mechanism for the rearrangement reactions of all tertiary phosphine complexes of type [RuX2L3 or 4] is proposed.Keywords
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