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Preparation, characterization and a kinetic study oftrans-[Ru(NH3)4L(H2O)](PF6)2 [L=PPh3, AsPh3, or SbPh3]

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Summary

The complexestrans-[Ru(NH3)4(H2O)PPh3](PF6)2 and [Ru(NH3)5L](PF6)2, (L=AsPh3 or SbPh3) have been isolated and characterized by microanalysis, cyclic voltammetry and ultraviolet-visible spectroscopy. The specific rate constants for the aquation of [Ru(NH3)5L]2+ totrans-[Ru(NH3)4L(H2O)]2+ are (2.5±0.1)×10−5s−1 and (1.8±0.1)×10−5s−1 for L=AsPh3 and SbPh3, respectively, at 25.0±0.1°C; μ=0.10 mol dm−3, NaO2CCF3. Under the same conditions, the second-order rate constants for the substitution of water intrans-[Ru(NH3)4(H2O)L]2+ by isonicotinamide (isn) are 1.2±0.1, (6.3±0.3)×10−2 and (3.8±0.2)×10−2 m −1s−1 for L=PPh3, AsPh3, and SbPh3, respectively, suggesting that the order of decreasingtrans-effect is: PPh3≫AsPh3>SbPh3. The formation constants for thetrans-[Ru(NH3)4L(isn)]2+ complexes are 75±3, (1.40±0.01)×103 and (1.80±0.02)×103M−1 for L=PPh3, AsPh3, and SbPh3, respectively, suggesting that the order of increasingtrans-influence is: SbPh3<AsPh3≪PPh3.

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Authors and Affiliations

  1. Instituto de Ciências Exatas, Universidade Federal de Minas Gerais, 30,000, Belo Horizonte, MG, Brasil

    José Milton de Rezende

  2. Instituto de Física e Química de São Carlos, Universidade de São Paulo, Caixa Postal 369, 13560, São Carlos, SP, Brasil

    Douglas Wagner Franco

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  1. José Milton de Rezende
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  2. Douglas Wagner Franco
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de Rezende, J.M., Franco, D.W. Preparation, characterization and a kinetic study oftrans-[Ru(NH3)4L(H2O)](PF6)2 [L=PPh3, AsPh3, or SbPh3]. Transition Met Chem 12, 267–270 (1987). https://doi.org/10.1007/BF01023546

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