Cleavage, heterolytic intramolecular

The first step of the reaction involves the dimerization of MPG via single electron transfer process by Ti(III) and the sequential Ti(IV)-catalyzed intramolecular heterolytic cleavage of the dimer, regenerating M PG and the nucleophilic radical (Equations 14.25 and 14.26). 

Intramolecular heterolytic cleavage of H2 is one of the oldest reactions of H2 and is among the first homogeneous catalytic conversions. r 2-H2 can protonate a counteranion or a basic ancillary ligand, either at the M-L bond or at a ligand lone pair. Intramolecular heterolysis of H H is most likely an essential step in many diverse systems ranging from industrial processes to the function of metallo enzymes such as... 

Nonclassical H-bonding has an important role in the intramolecular heterolytic cleavage of H2 in these complexes (as illustrated in Scheme 4.15). H-bonding between the internal base and the / -H2 ligand stabiHzes the complex... 

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