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Exchange kinetics for the decomplexation reaction of sodium tetraphenylborate complexes by the ligand monobenzo-15-crown-5 in nitromethane have been studied by 23Na nuclear magnetic resonance.The predominant mechanism for the sodium exchange is bimolecular and is characterized by the following activation parameters: DeltaH<*> = 28 +/- 3 kJ.mol-1, DeltaS<*> = -57 +/- 10 J.mol-1.K-1, and DeltaG<*>300 = 45 +/- 3 kJ.mol-1.A coalescence was observed for a sodium concentration of 4.0 x 1E-2 M (300 K).At low sodium concentrations the unimolecular decomplexation mechanism becomes competitive.It is characterized by DeltaG<*>300 = 62 +/- 6 kJ.mol-1.
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