Journal
COORDINATION CHEMISTRY REVIEWS
Volume 376, Issue -, Pages 478-505Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ccr.2018.08.011
Keywords
Copper; Phenanthroline; Diimine; Kinetics; Rate; Molecular machines; Devices; Switches
Categories
Funding
- Deutsche Forschungsgemeinschaft [DFG 647/19-2, DFG 647/20-1]
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Two and a half decades of copper phenanthroline-based switches, devices and machines have illustrated the rich dynamic nature of these metal complexes. With an emphasis on the metal-ligand dissociation as the rate-determining step the present review summarizes not only spectacular examples of machinery, but also highlights rate data collected during a variety of investigations. Copper-ligand exchange reactions are mostly triggered by redox processes, addition of metal ions or addition of ligands. While the rate data spread over >8 orders of magnitude, individual effects of solvent, steric bulk, flexibility, sigma-basicity and the trajectory (intra- vs. intermolecular dissociation) have large impact. Unfortunately, in many cases the exact mechanism in the rate-determining step (nucleophile-induced vs. monomolecular metal-ligand dissociation) has not been determined, suggesting to invest further efforts in the physical (in)organic chemistry of such coordination-driven systems. (C) 2018 Elsevier B.V. All rights reserved.
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