Hydrogen, molecular transfers

The stereoselectivity of this reaction depends on how the alkene approaches the catalyst surface As the molecular model m Figure 6 3 shows one of the methyl groups on the bridge carbon lies directly over the double bond and blocks that face from easy access to the catalyst The bottom face of the double bond is more exposed and both hydrogens are transferred from the catalyst surface to that face... 

Water-soluble complexes constitute an important class of rhodium catalysts as they permit hydrogenation using either molecular hydrogen or transfer hydrogenation with formic acid or propan-2-ol. The advantages of these catalysts are that they combine high reactivity and selectivity with an ability to perform the reactions in a biphasic system. This allows the product to be kept separate from the catalyst and allows for an ease of work-up and cost-effective catalyst recycling. The water-soluble Rh-TPPTS catalysts can easily be prepared in situ from the reaction of [RhCl(COD)]2 with the sulfonated phosphine (Fig. 15.4) in water [17]. 

This simplified description of molecular transfer of hydrogen from the gas phase into the bulk of the liquid phase will be used extensively to describe the coupling of mass transfer with the catalytic reaction. Beside the Henry coefficient (which will be described in Section 45.2.2.2 and is a thermodynamic constant independent of the reactor used), the key parameters governing the mass transfer process are the mass transfer coefficient kL and the specific contact area a. Correlations used for the estimation of these parameters or their product (i.e., the volumetric mass transfer coefficient kLo) will be presented in Section 45.3 on industrial reactors and scale-up issues. Note that the reciprocal of the latter coefficient has a dimension of time and is the characteristic time for the diffusion mass transfer process tdifl-GL=l/kLa (s). 

The occurrence of the McLafferty rearrangement is strictly limited to molecular ions possessing at least one y-hydrogen for transfer to the terminal atom at the double bond. Thus, blocking the y-position, e.g., by introduction of alkyl or halogen substituents, effectively hinders this dissociation pathway. 

For aminophenols, one-electron oxidation and the proton elimination can run together in one stage. This leads to a cation-radical containing O and +NH3 fragments within one and the same molecular carcass (Rhile et al. 2006). Such concerted reactions are classified as proton-coupled electron transfer (Mayer 2004). Proton-coupled electron transfer differs from conventional one-electron redox reaction in the sense that proton motion affects electron transfer. Because the transfers of a proton and an electron proceed in a single step, we can say about the hydrogen-atom transference, (H+ -I- e)=H. It is the fundamental feature of proton-coupled electron-transfer reactions that the proton and electron are transferred simultaneously, but from different places (see Tanko 2006). 

Alkyl radicals higher than methyl can undergo two competing bi-molecular termination reactions (a) combination to give a saturated dimer (reaction 35) and (b) disproportionation to give an alkene and an alkane by a hydrogen atom transfer from one radical to another (reaction 36). 

The first reaction involves interaction of a hydrocarbon with the catalyst surface. Hydride abstraction occurs to form a carbonium ion. Abstraction can be of any suitable hydrogen atom but if this results in a primary ion as shown, this will rapidly isomerise by hydrogen shift to the more thermodynamically stable secondary ion. This may be further isomerised by carbon shift to a tertiary ion. This contrasts with free radicals and although isomerisation occurs it is relatively slower. The carbonium ions can also undergo inter-molecular transfer (not shown) when a carbonium ion meets another hydrocarbon molecule. 

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