A dissociative substitution loses a ligand before binding the incoming replacement. A saturated 18-electron carbonyl can first form a 16-electron intermediate; the dissociation barrier and intermediate rearrangement influence rates and product geometry.
The carbonyl cis effect is preferential labilization of a ligand cis to another ligand in many six-coordinate metal carbonyls. Site preference in five-coordinate intermediates and transition states matters. Isotopic exchange can distinguish departure sites more directly than substitution-product geometry alone.
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