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Comparing the Isoelectronic Complexes [RuTp(CH<sub>3</sub>CN)<sub>3</sub>]PF<sub>6</sub> (Tp = Hydridotris(pyrazolyl)borate) and [RuCp(CH<sub>3</sub>CN)<sub>3</sub>]PF<sub>6</sub>. Structure and Acetonitrile Exchange Kinetics
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Citations
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References
1999
Year
Inorganic ChemistryChemical EngineeringEngineeringBiochemistryNatural SciencesCoordination ComplexFirst-order Rate ConstantCh3cn Exchange KineticsAcetonitrile Exchange KineticsMolecular ComplexChemistryMuch Higher EnergyMolecular ChemistryChemical KineticsInorganic Compound
The cationic trisacetonitrile complex [RuTp(CH3CN)3]PF6 has been obtained in 70% isolated yield by the reaction of RuTp(COD)Cl with NH4PF6 in boiling DMF/CH3CN. The CH3CN exchange kinetics has been studied by 1H NMR as a function of temperature. The first-order rate constant of 1.2 × 10-8 s-1 (298 K) is very low compared to 5.6 s-1 for the isoelectronic [RuCp(CH3CN)3]PF6, essentially because of a much higher energy of activation (37.2 vs 20.7 kcal mol-1).
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