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This content will become publicly available on August 16, 2024

Title: Catalytic Inhibition of Base‐Mediated Reactivity by a Self‐Assembled Metal‐Ligand Host
Abstract

Spacious M4L6tetrahedra can act as catalytic inhibitors for base‐mediated reactions. Upon adding only 5 % of a self‐assembled Fe4L6cage complex, the conversion of the conjugate addition between ethylcyanoacetate and β‐nitrostyrene catalyzed by proton sponge can be reduced from 83 % after 75 mins at ambient temperature to <1 % under identical conditions. The mechanism of the catalytic inhibition is unusual: the octacationic Fe4L6cage increases the acidity of exogenous water in the acetonitrile reaction solvent by favorably binding the conjugate acid of the basic catalyst. The inhibition only occurs for Fe4L6hosts with spacious internal cavities: minimal inhibition is seen with smaller tetrahedra or Fe2L3helicates. The surprising tendency of the cationic cage to preferentially bind protonated, cationic ammonium guests is quantified via the comprehensive modeling of spectrophotometric titration datasets.

 
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Award ID(s):
2002619
NSF-PAR ID:
10468073
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Chemistry – A European Journal
Volume:
29
Issue:
63
ISSN:
0947-6539
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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