Single-site hydrogen-bond modulation enhances catalytic ester hydrolysis in a Zn( ii )–TPA scaffold
Abstract
OH group acts as a precisely positioned secondary-sphere hydrogen-bond donor that does not bind Zn(II) directly but reshapes the local microenvironment. This modification facilitates hydrogen transfer, stabilizes the transition state, and enhances nucleophilic activation of the Zn-bound water molecule. Structural data support an intramolecular hydrogen-bonding network consistent with this mechanistic role. As a result, the engineered complex exhibits a dramatic rate enhancement-over an order of magnitude faster than the parent Zn(II)-TPA system-demonstrating the powerful catalytic impact of secondary-sphere engineering in artificial metalloenzymes.
Fields of Study & Subjects
Cyclopropane Reaction Mechanisms
Supramolecular Chemistry and Complexes
Metal-Catalyzed Oxygenation Mechanisms
Publication details
- Journal / source
- Dalton Transactions
- Publisher
- Royal Society of Chemistry (RSC)
- Volume
- 55
- Issue
- 12
- Pages
- 5004–5012
- Publication date
- 1 January 2026
- Language
- EN