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The cobalt(III) pentammine complex, [Co(NH3)5Cl]2+, consists of a central cobalt cation with coordinate covalent bonds to five neutral ammonia molecules and a chloride anion, which act as ligands.  In an aqueous solution with a pH > 10, the complex readily undergoes a ligand exchange via base hydrolysis as shown in Reaction 1.[Co(NH3)5Cl]2++OH−⟶[Co(NH3)5(OH)]2++Cl−CoNH35Cl2++OH-⟶CoNH35OH2++Cl-Reaction 1Researchers have proposed that Reaction 1 might proceed by either a bimolecular nucleophilic substitution (an SN2 mechanism) as shown in Figure 1, or by a unimolecular nucleophilic substitution of the complex's conjugate base (an SN1CB mechanism) as shown in Figure 2.Figure 1  SN2 mechanism proposed for Reaction 1Figure 2  SN1CB mechanism proposed for Reaction 1In the proposed SN2 mechanism, the OH− ion functions as a nucleophile that attacks the central Co atom in the complex.  Accordingly, the nucleophilic attack results in a transition state in which the existing Co–Cl bond breaks and a new Co–OH bond forms in a single step.In contrast, the SN1CB mechanism proposes that the reaction occurs in multiple steps in which OH− initially acts as a base to deprotonate one of the coordinately bonded ammine ligands to form a hexa-coordinated intermediate with an amido (NH2−) ligand (Step 1).  The Cl− ligand in the amido intermediate then dissociates to form a pentacoordinated intermediate (Step 2).  A water molecule from the solution then coordinates with the Co atom of the pentacoordinated intermediate to form an aquo complex (Step 3).  A solvent-mediated proton transfer from the aquo to the amido ligand yields the final base-hydrolysis product (Step 4). Question 38To evaluate the proposed mechanisms, researchers attempted to modify Reaction 1 by replacing the [Co(NH3)5Cl]2+ complex with the complex shown above, which contains C5H5N (pyridine) ligands instead of NH3 ligands, but no reaction occurred.  Assuming that steric hindrance is not a factor in the reaction, this result provides evidence in support of the:A.SN2 mechanism, because the experimental change resulted in no reaction.B.SN2 mechanism, because the pyridine ligands have a negative formal charge that repels the OH− ion.C.SN1CB mechanism, because the leaving group is the same in both the original and the modified reaction.D.SN1CB mechanism, because an N–H bond is required to form the proposed intermediate.

Question

The cobalt(III) pentammine complex, [Co(NH3)5Cl]2+, consists of a central cobalt cation with coordinate covalent bonds to five neutral ammonia molecules and a chloride anion, which act as ligands.  In an aqueous solution with a pH > 10, the complex readily undergoes a ligand exchange via base hydrolysis as shown in Reaction 1.[Co(NH3)5Cl]2++OH−⟶[Co(NH3)5(OH)]2++Cl−CoNH35Cl2++OH-⟶CoNH35OH2++Cl-Reaction 1Researchers have proposed that Reaction 1 might proceed by either a bimolecular nucleophilic substitution (an SN2 mechanism) as shown in Figure 1, or by a unimolecular nucleophilic substitution of the complex's conjugate base (an SN1CB mechanism) as shown in Figure 2.Figure 1  SN2 mechanism proposed for Reaction 1Figure 2  SN1CB mechanism proposed for Reaction 1In the proposed SN2 mechanism, the OH− ion functions as a nucleophile that attacks the central Co atom in the complex.  Accordingly, the nucleophilic attack results in a transition state in which the existing Co–Cl bond breaks and a new Co–OH bond forms in a single step.In contrast, the SN1CB mechanism proposes that the reaction occurs in multiple steps in which OH− initially acts as a base to deprotonate one of the coordinately bonded ammine ligands to form a hexa-coordinated intermediate with an amido (NH2−) ligand (Step 1).  The Cl− ligand in the amido intermediate then dissociates to form a pentacoordinated intermediate (Step 2).  A water molecule from the solution then coordinates with the Co atom of the pentacoordinated intermediate to form an aquo complex (Step 3).  A solvent-mediated proton transfer from the aquo to the amido ligand yields the final base-hydrolysis product (Step 4). Question 38To evaluate the proposed mechanisms, researchers attempted to modify Reaction 1 by replacing the [Co(NH3)5Cl]2+ complex with the complex shown above, which contains C5H5N (pyridine) ligands instead of NH3 ligands, but no reaction occurred.  Assuming that steric hindrance is not a factor in the reaction, this result provides evidence in support of the:A.SN2 mechanism, because the experimental change resulted in no reaction.B.SN2 mechanism, because the pyridine ligands have a negative formal charge that repels the OH− ion.C.SN1CB mechanism, because the leaving group is the same in both the original and the modified reaction.D.SN1CB mechanism, because an N–H bond is required to form the proposed intermediate.

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Solution

The correct answer is D. SN1CB mechanism, because an N–H bond is required to form the proposed intermediate.

In the SN1CB mechanism, the first step involves the deprotonation of one of the NH3 ligands to form an amido (NH2-) ligand. This step is crucial for the mechanism to proceed. In the modified reaction, the NH3 ligands are replaced with pyridine (C5H5N) ligands. Pyridine does not have a hydrogen atom attached to the nitrogen, so it cannot be deprotonated in the same way as NH3. Therefore, the first step of the SN1CB mechanism cannot occur, and the reaction does not proceed. This provides evidence in support of the SN1CB mechanism.

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