Abstract
trans-[Co(CH2Cl)(tmsalen)(S)] undergoes metallacyclization in water/methanol, affording the cis β organometallic derivative [Co(tmsalenCH2)(S)2]Cl. The presence of N-donor ligands, L, increases the cyclization rate mainly by electronic effects. The reaction involves the substitution of the solvent by L in a fast preequilibrium step, both [Co(CH2Cl)(tmsalen)(S)] and [Co(CH2Cl)(tmsalen)(L)] undergoing the cyclization reaction. As the cyclization involves the formation of ions from a neutral complex, the large negative activation entropy is attributed to the freezing of the solvent around the incipient ions in the transition state.
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