Mechanisms of organometallic substitution reactions. Part 4. Kinetics of replacement of dimethyl sulphoxide (dmso) from [RuX2(η-C6H6)(dmso)](X = Cl or Br) complexes by triphenylphosphine
- 1 January 1981
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 4,p. 923-927
- https://doi.org/10.1039/dt9810000923
Abstract
A kinetic study has been undertaken of the replacement of dimethyl sulphoxide (dmso) in [RuX2(η-C6H6)(dmso)](X = Cl or Br) by triphenylphosphine in both dmso and 1,2-dichloroethane as solvent [equation (1)]. For the [RuX2(η-C6H6)(dmso)]+ PPh3→[RuX2(η-C6H6)(PPh3)]+ dmso (1) relatively slow reactions in dmso the rate law, rate =K[complex][PPh3], is observed. However, a stopped-flow kinetic investigation of the rapid reactions in 1,2-dichloroethane supports a rate law of the form: rate =k1k2-[complex][PPh3]/(k–1[dmso]+k2[PPh3]). For both solvents a mechanism is proposed involving initial dissociation (k1) of the dmso ligand generating the co-ordinatively unsaturated intermediates, [RuX2(η-C6H6)], which may then either recombine (k–1) with dmso to regenerate the starting complexes or add a PPh3 ligand irreversibly (k2) to yield the observed products.Keywords
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