By M.M. Taqui Khan
Activation Of Small Inorganic Molecules
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Extra info for Activation of Small Inorganic Molecules
Since there was a slight change in the rotation of the final product it was assumed that there should be two retentions or two inversions in the process of addition of the optically active ester to the iridium complex and subsequent cleavage. Since the cleavage of alkyl-metal bonds by bromine was found to proceed with retention of configuration , it was argued that the addition of ester to the metal ion should also proceed with retention of configuration. In view of these findings, it was suggested  that the process of oxidative addition of alkyl halides to the iridium(I) complexes occurs by a one-step concerted process without the formation of intermediates and with the rentention of configuration of the alkyl carbon atom.
This order of addition of catalyst to the solution ensures better dissolution of the catalyst without dimerization to [RhCl(PPh 3 ) 2 ] 2 . The solution is maintained saturated with respect to hydrogen at all times. The addition of a polar solvent such as ethanol or a ketone to benezene sufficiently accelerates the rate of hydrogénation, although no correlation could be found between the dielectric constant of the polar solvent (co-catalyst) and the reaction rate. Catalysis of the hydrogénation of the alkenes by rhodium(I) may take place by two paths, A and B, indicated in the following reaction scheme.
5, trans-2-butene is the main (86%) reaction product. With a [CN"]/[Co] ratio of 6 or more, however, 1-butene predominates. The dependence of isomer distribution on [CN~]/[Co] ratio was explained by Kwiatek  on the basis of the formation of different σ and π intermediates 3 in the reaction of [HCo(CN) 5] ~ with butadiene. 5) a ττ-allyl complex, 25 (see Scheme I) is formed which gives trans-2-butene as the main reaction product. The formation of the ττ-allyl complex 25 requires that the conjugated diene should be able to assume a "cissoid" conformation.
Activation of Small Inorganic Molecules by M.M. Taqui Khan