This investigation explored whether there is a spin barrier to recombination of first- and second-row transition metal-centered radicals in a radical cage pair. To answer this question, the recombination efficiencies of photochemically generated radical cage pairs (denoted as FcP) were measured in the presence and absence of an external heavy atom probe. Two methods were employed for measuring the cage effect. The first method was femtosecond pump-probe transient absorption spectroscopy, which directly measured FcP from reaction kinetics, and the second method (referred to herein as the "steady-state" method) obtained FcP from quantum yields for the radical trapping reaction with CCl4 as a function of solvent viscosity. Both methods generated radical cage pairs by photolysis (lambda = 515 nm for the pump probe method and lambda = 546 nm for the steady-state method) of Cp'2Mo2(CO)6 (Cp' = eta(5)-C5H4CH3). In addition, radical cage pairs generated from Cp'2Fe2(CO)4 and Cp*2TiCl2 (Cp* = eta(5)-C5(CH3)5) were studied by the steady-state method. The pump-probe method used p-dichlorobenzene as the heavy atom perturber, whereas the steady-state method used iodobenzene. For both methods and for all the radical caged pairs investigated, there were no observable heavy atom effects, from which it is concluded there is no spin barrier to recombination.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.