Hydrogen-deuterium exchange, catalyzed

From the few results published, it would appear that the mechanistic pathway for hydrogen-deuterium exchange catalyzed by rhodium(III), iridium(III), and ruthenium(II) is the same as for platinum(II). 

Several authors have reported that they did not succeed in isolating a number of pseudoazulenes when solutions in dilute mineral or glacial acetic acids were diluted with water or other bases.51-71,77-86 It was only possible to recover polymer-like material. In the subsequent decomposition the nucleophile attacks the conjugated acid of the pseudoazulenes at a position adjacent to the heteroatom, probably resulting in a fission. The hydrogen-deuterium exchange catalyzed by acids has been reported for systems 29,86 31,86 and 49.135... 

The reaction takes place extremely rapidly and if D2O is present in excess all the alcohol is con verted to ROD This hydrogen-deuterium exchange can be catalyzed by either acids or bases If D30 is the catalyst in acid solution and DO the catalyst in base wnte reasonable reaction mech anisms for the conversion of ROH to ROD under conditions of (a) acid catalysis and (b) base catalysis... 

In pyridazine, base-catalyzed hydrogen-deuterium exchange takes place at positions 4 and 5 more easily than at positions 3 or 6. Deuteration of pyridazine 1-oxide in NaOD/DiO... 

The choice of solvent can also be beneficial in another respect. This possibility was highlighted by the findings of Cioffi on the Raney Nickel catalyzed hydrogen-deuterium exchange of a model carbohydrate [l-0-methyl-/l-D-galactopyranoside] but under ultrasonic irradiation (Tab. 13.2) [43], Extensive deuteration at C-4 position occurred for a series of ethereal solvents, the C-3 position was deuterated by seven solvent systems and the C-2 position deuterated less extensively, also by seven solvent systems. For l,4-dioxane-D20 no labeling at the C-2 position occurred and for l,2-dimethoxyethane-D20 no C-3 labeling was observed. 

Dicobalt octacarbonyl and bis(triphenylphosphine)carbonyl chloroiri-dium catalyzed analogous hydrogen-deuterium exchanges (28). 

Harrison and McDowell 138) observed that while neither zinc oxide nor a, o-dip enyl-/3-picryl hydrazyl (a solid free radical) alone, catalyze hydrogen-deuterium exchange measurably at 77° K, a mixture of the two solids possesses considerable catalytic activity. They suggested that the effective catalyst in this mixture is the zinc oxide and that its catalytic activity is enhanced by electron transfer to the a,a-diphenyl-/3-picryl hydrazyl. It should be noted, however, that this implies a dependence of catalytic activity on electron concentration which is opposite to that observed by Molinari and Parravano 134). To bring the results for this system into line with those obtained by the latter workers, it would be necessary to postulate electron transfer in the opposite direction, i.e., from the a, a-diphenyl-/8-picryl hydrazyl to the zinc oxide. ... 

In this connection, the dependence of the rate of the hydrogen-deuterium exchange reaction catalyzed by zinc oxide, upon the concentration of a foreign oxide in ZnO is interesting. This system was investigated by Molinari and Parravano (94). As shown in Fig. 16, the rate of... 

The a-carbon-hydrogen bonds of vinyl(phenyl)iodonium ions are relatively acidic, two examples of base catalyzed hydrogen-deuterium exchange in -oxavinyliodonium salts having been reported (equations 227 and 228)79,95. Although vinylidene-iodonium ylides... 

Rate Data for Base-Catalyzed Hydrogen-Deuterium Exchange... 

---