Abstract
The 16-electron fragment [(triphos)IrH], generated in situ by thermolysis of (triphos)Ir(H) 2(C 2H 5) in THF, reacts with thiophene ( T) or benzo[ b]thiophene ( BT) to give, in the temperature range from 67 to 100°C, mixtures of CH and CS insertion product as a result of parallel reactions [triphos = MeC(CH 2PPh 2) 3]. Above 100°C, the (thienyl)dihydride complexes convert to the thermodynamically more stable CS insertion products (butadienethiolate and 2-vinylthiophenolate complexes) through an intramolecular mechanism which does not involve T or BT dissociation. A comparison is made to analogous reactions with dibenzothiophene.
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