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Steady-State and Pseudo-Steady-State Photocrystallographic Studies on Linkage Isomers of [Ni(Et4dien)(h2-O,ON)(h1-NO2)]: Identification of a New Linkage Isomer
DOI:
10.1002/chem.201304172
PMID:
24519880
Authors:
Lauren
Hatcher
(University of Bath)
,
Jeppe
Christensen
(Lund University)
,
Michelle
Hamilton
,
Jose
Trincao
(University of Bath)
,
Dave
Allan
(Diamond Light Source)
,
Ian P.
Clarke
(Central Laser Facility, STFC Rutherford Appleton Laboratory)
,
Mike
Towrie
(Research Complex at Harwell)
,
Sara
Fuertes
(University of Bath)
,
Charles C.
Wilson
(University of Bath)
,
Christopher
Woodall
(University of Bath)
,
Paul
Raithby
(University of Bath)
,
Mark
Warren
(Diamond Light Source)
Co-authored by industrial partner:
No
Type:
Journal Paper
Journal:
Chemistry - A European Journal
State:
Published (Approved)
Published:
February 2014
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.
Journal Keywords: Linkage Isomers · Metastable States · Nitro Complexes · Photocrystallography · Solid-State Kinetics
Subject Areas:
Chemistry
Instruments:
I19-Small Molecule Single Crystal Diffraction