Easing Intermediates Search by Combining Spectroscopy and Multivariate Curve Reconstruction:
Gabriele Deplano1, Isabelle Gerz2, Derya Demirbas3
1Department of Chemistry, NIS and INSTM Reference Centre, Università di Torino, Via P. Giuria 7, 10125 and Via G. Quarello 15/A, 10135 Torino, Italy.
Abstract:
Despite their prevalence in catalysis, complex reaction mixtures are not trivial to investigate and disentangle. Different approaches can be applied to characterize them, even featuring low-dimensionality data sets. The liquid-phase reaction of [CuI(6,6'-dimethyl-2,2'-bipyridyl)2]PF6 (Cu) with tert-butyl hydroperoxide is investigated: two CuII species are found upon oxidation of the pristine complex, characterized by different spectroscopic and kinetics fingerprints. Coupling EPR and UV-vis spectroscopies with chemometric methods (namely, multivariate curve reconstruction, MCR) allowed for easily retrieving pure spectral features and concentration profiles. Spectrokinetic analysis independently showed an optimal agreement with kinetic outcomes from MCR. Finally, hypotheses on the nature of the CuII species are drawn on the basis of EPR fitting and quantum chemistry computations on a series of candidate structures. Beyond the accurate characterization of a model system, this study demonstrates the potential of coupling multivariate statistical techniques, experiments, and computations toward a quantitative understanding of electronic and kinetic information on complex chemical systems.
Related Concept Videos
¹H NMR: Complex Splitting
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied...
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
Woodward–Hoffmann Selection Rules and Microscopic Reversibility
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism
UV–Vis Spectroscopy: Woodward–Fieser Rules

![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
