Ruthenium complexes containing Group 5B donor ligands. Part 3. Rearrangement reactions of some ruthenium(II) carbonyl and thiocarbonyl triphenylphosphine complexes
- 1 January 1976
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 20,p. 2121-2128
- https://doi.org/10.1039/dt9760002121
Abstract
Reaction of [RuCl2(PPh3)3] with [Ru(CO)Cl2(dmf)(PPh3)2] in acetone (1: 1 molar ratio)(dmf =NN-dimethylformamide) gives a high yield of [(Ph3P)2ClRuCl3Ru(CO)(PPh3)2]·2Me2CO, supporting the mechanism proposed earlier for formation of the analogous thiocarbonyl complex. Extensions of this type of coupling reaction to form [(Ph3P)2BrRuBrCl2Ru(CO)(PPh3),]·Me2CO and [(Ph3P)2ClRuBr2ClRu(CO)(PPh3)2]·Me2CO are also described. Recrystallisation of [Ru(CO)Cl2(dmf)(PPh3)2] from MaOH–CH2Cl2 gives [Ru(CO)Cl2(HOMe)(PPh3)2](4), and prolonged refluxing of the latter in dichloromethane–light petroleum (b.p. 60–80 °C) produces displacement of a PPh3 group with formation of an isomeric mixture of [(Ph3P)Cl(OC)RuCl3Ru(CO)(PPh3)2](5). The same isomeric mixture, together with [{Ru(CO)Cl2(PPh3)2}2], is also formed by reaction of PPh3 with [PPh3(CH2Ph)][Ru(C7H8)(CO)Cl3](2 : 1 molar ratio). Treatment of (5) with Na[BPh4] and PPh3 in CH2Cl2 gives a high yield of [(Ph3P)2(OC)RuCl3Ru(CO)(PPh3)2][BPh4](6). This cation is also formed, together with (5), by prolonged shaking of (4) in ethanol, whereas treatment of (4) with [AsPh4]Cl·HCl in acetone gives [AsPh4][Ru(CO)Cl3(PPh3)2]·Me2CO (7). Related complexes are described, starting from [Ru(CS)Cl2(dmf)(PPh3)2]. Finally, all this information is used to suggest detailed rearrangement mechanisms in the [RuCl2(PPh3)3]–CS2, [PPh3(CH2Ph)][Ru(C7H8)(CO)Cl3]–2PPh3, and the closely related [RuX2(PR3)n]–[Ru2X3(PR3)6]X (X = Cl or Br; n= 3 or 4) systems.Keywords
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