By M.M. Taqui Khan
Activation Of Small Inorganic Molecules
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Extra info for Activation of Small Inorganic Molecules
For complexes of 49 VIII. HYDROGENATION OF π COMPLEXES Η PPh3 •PPh3 Rh Η2 4 Rh^ (A) •PPh3 -PPh3 CI" 40 39 + olefin (B) olefin K2 a- •PPh 3 Rh" 1 H- PPh3 „ Rh H PPh3 PPh3 ci41 42 39 + paraffin the type [RhCl(PPh 3) 2L], where L is carbon monoxide or ethylene (strong πacids), the reduction of the electron density around the metal ion by back donation raises the oxidation potential of the Rh(I)/Rh(III) couple; hence activation of molecular hydrogen is inhibited. The ability of IrX(PPh 3 ) 2 CO to activate molecular hydrogen  is due to a lower oxidation potential of the Ir(I)/Ir(III) couple as compared to the Rh(I)/Rh(III) couple.
It is possible that such reactions may proceed via platinum(IV) or palladium(IV) intermediates formed by intramolecular oxidative addition of hydride and σ-carbon-bonded moieties, followed by a reductive elimination of hydrogen chloride from platinum(IV) or palladium(IV) complexes to give corresponding platinum(II) or palladium(II) complexes. A very interesting reaction involving catalysis of hydrogen-deuterium 2 exchange of saturated hydrocarbons, C n H 2 n + 2( t f = 1-6) with PtCl 4 ~ has been reported by Hodges et al.
8 A five-coordinate monohydrido d complex of iridium(I), IrH(CO)(PPh 3) 3, catalyzes the hydrogénation of ethylene and acetylene at much faster rates than does the corresponding square-planar complex, Ir(CO)X(PPh 3) 2 . 55 VIII. H Y D R O G E N A T I O N O F π COMPLEXES The formation of a seven-coordinate complex by oxidative addition of hydrogen to the iridium(I) complex was suggested [Eq. (67)]. IrH(CO)(PPh 3) 3 + H 2 Ir(H) 3(CO)(PPh 3)3 (67) A six-coordinate iridium(I) complex with the olefin as a ligand was also proposed [Eq.
Activation of Small Inorganic Molecules by M.M. Taqui Khan