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- W2105147805 abstract "The reaction of [Ir2Rh2(CO)12] with 1 mol-equiv. of PPh3 yields [Ir2Rh2(CO)11PPh3] (1) as a mixture of two isomers with the phosphine ligand axially bound either to one basal Rh-atom in the kinetically preferred isomer 1 R or to one basal Ir-atom in the thermodynamically preferred isomer 11. Both isomers are fluxional on the 13C-NMR time scale at low temperature due to CO scrambling. Around room temperature, a new type of fluxional process starts to operate which is responsible for the isomerisation 1R⇄11, i.e. the intramolecular migration of the reputedly inert PPh3 ligand from one metal centre to another. The activation volumes of conversions 1R → 11 and 11 → 1R are both positive, indicating that the migration of PPh3 is dissociative in character. This article reports the first application of variable pressure 31P-NMR to mechanistic studies." @default.
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- W2105147805 date "1994-03-23" @default.
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- W2105147805 title "Variable-Temperature and -Pressure31P-NMR Study of the Intramolecular PPh3 Migration in the Cluster Compound [Ir2Rh2(CO)11PPh3]" @default.
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- W2105147805 doi "https://doi.org/10.1002/hlca.19940770216" @default.
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