Abstract
Reactions between [Re(X)(CO)3(bipy)] (X = OH, OMe, NHpTol, PPh2; bipy = 2,2'‐bipyridine) complexes and methyl propiolate (HMAD) are studied to rationalize the different products experimentally obtained. Three reaction patterns were found with a common and limiting initial attack of X to HMAD. Thus, the experimental selectivity depends on the kinetics and/or thermodynamics of the last reaction stages. For X = OH and NHpTol an easy intramolecular attack of the X‐linked HMAD to a highly electrophilic CO ligand is followed by a hydrogen transposition to this CO, yielding very stable species (C‐CCOH products). When X = OMe, the insertion of the X‐attached HMAD into the Re–OMe bond (ins product) takes place due to the smallest barrier and the largest stability of the ins route. Finally, when X = PPh2 the ins route becomes restricted and the route for the coupling of the X‐attached HMAD with bipy (C‐Cbipy product) wins over the one for the coupling with CO (C‐CCO product) only due to the larger stability of the C‐Cbipy product.
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