Binuclear ‘oxidative isomerization’ as a model for surface reactions. Intramolecular character and kinetic profile of iodomethyldi-iridium(II): µ-methylenedi-iridium(III) conversion that follows di-iodomethane addition to [Ir(CO)(PPh3)(µ-pz)]2(Hpz = pyrazole)
- 1 January 1989
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Chemical Communications
- No. 8,p. 498-500
- https://doi.org/10.1039/c39890000498
Abstract
Isomerization of the di-iridium(II) complex [Ir2(CO)2(PPh3)2(µ-pz)2(CH2I)(I)](2, Hpz = pyrazole) to the di-iridium(III) methylene complex [Ir2(CO)2(PPh3)2(µ-pz)2(µ-CH2)(I)2](7) which occurs on reflux in benzene solution has been found to be intramolecular by mass spectrometric analysis of isotope distribution (13C and 2H) in isotopomers of (7) formed from (2) containing 13CO or C2H2I groups or both, and the (2)–(7) conversion shows first-order behaviour which is conspicuously retarded by added PPh3; an X-ray crystal structure determination for compound (7) confirms that the two Ir centres lie outside bonding range at 3.432(1)Å with tetrahedral µ-CH2.Keywords
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