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Title: Kinetics of the Same Reaction Monitored over Nine Orders of Magnitude in Concentration: When Are Unique Subensemble and Single-Turnover Reactivity Displayed?

Journal Article · · Angewandte Chemie (International Edition)

Abstract Essentially no information is known about the behavior of individual molecular catalysts under reaction conditions. This is a result of the averaging inherent to traditional analytical techniques. Herein, a combined fluorescence microscopy and 1 H NMR spectroscopy study reveals that unique (that is, non‐ensemble averaged) distributions and time‐variable kinetics from molecular ruthenium catalysts within growing polynorbornene occur and are detectable between 10 −9   m and 10 −6   m of substrate, surprisingly just 1000‐fold less concentrated than a typical laboratory bench‐scale reaction. The kinetic states governing single‐turnover events are determinable by overlay of the signal arising from individual monomer insertion reactions with that from polymer growth from neighboring catalysts.

Research Organization:
Univ. of California, Irvine, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0016467
OSTI ID:
1836115
Alternate ID(s):
OSTI ID: 1463361
Journal Information:
Angewandte Chemie (International Edition), Vol. 57, Issue 37; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

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Cited By (2)

Kinetics of initiation of the third generation Grubbs metathesis catalyst: convergent associative and dissociative pathways journal January 2019
Sialic acid–targeted drug delivery and imaging system for pH- and glutathione-triggered multiple anticancer drug release and enhanced oxidative stress journal April 2020