ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19940770216
