Steady‐state and pseudo‐steady‐state photocrystallographic studies on linkageiIsomers of [Ni(Et4dien)(η2‐O,ON)(η1‐NO2)]: identification of a new linkage isomer

Hatcher, Lauren E. ORCID: https://orcid.org/0000-0002-1549-9727, Christensen, Jeppe, Hamilton, Michelle L., Trincao, Jose, Allan, David R., Warren, Mark R., Clarke, Ian P., Towrie, Michael, Fuertes, Dr Sara, Wilson, Charles C., Woodall, Christopher H. and Raithby, Paul R. 2014. Steady‐state and pseudo‐steady‐state photocrystallographic studies on linkageiIsomers of [Ni(Et4dien)(η2‐O,ON)(η1‐NO2)]: identification of a new linkage isomer. Chemistry - A European Journal 20 (11) , pp. 3128-3134. 10.1002/chem.201304172

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Abstract

At temperatures below 150 K, the photoactivated metastable endo‐nitrito linkage isomer [Ni(Et4dien)(η2‐O,ON)(η1‐ONO)] (Et4dien=N,N,N′,N′‐tetraethyldiethylenetriamine) can be generated with 100 % conversion from the ground state nitro‐(η1‐NO2) isomer on irradiation with 500 nm light, in the single crystal by steady‐state photocrystallographic techniques. Kinetic studies show the system is no longer metastable above 150 K, decaying back to the ground state nitro‐(η1‐NO2) arrangement over several hours at 150 K. Variable‐temperature kinetic measurements in the range of 150–160 K show that the rate of endo‐nitrito decay is highly dependent on temperature, and an activation energy of Eact=+48.6(4) kJ mol−1 is calculated for the decay process. Pseudo‐steady‐state experiments, where the crystal is continually pumped by the light source for the duration of the X‐ray experiment, show the production of a previously unobserved, exo‐nitrito‐(η1‐ONO) linkage isomer only at temperatures close to the metastable limit (ca. 140–190 K). This exo isomer is considered to be a transient excited‐state species, as it is only observed in data collected by pseudo‐steady‐state methods.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	Wiley
ISSN:	0947-6539
Date of First Compliant Deposit:	18 March 2020
Date of Acceptance:	12 February 2014
Last Modified:	06 May 2023 00:30
URI:	https://orca.cardiff.ac.uk/id/eprint/130475

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