136157-01-2Relevant articles and documents
Steric vs electronic effects and solvent coordination in the electrochemistry of phenanthroline-based copper complexes
Magni, Mirko,Colombo, Alessia,Dragonetti, Claudia,Mussini, Patrizia
, p. 324 - 330 (2014)
The present exhaustive electrochemical study proposes a rationalization of the redox properties of 1,10-phenanthroline-based copper complexes as a function of i) ligand molecular structure, evidencing the competition between electronic and steric effects of alkyl/aryl substituents, and ii) nature of working medium in terms of both solvent and supporting electrolyte anion. Occupancy of the 2 and 9 positions of the phenanthroline is a powerful tool to modulate the oxidation potentials of this family of complexes in a wide potential range. Solvent molecules play a key role in the metal-centred oxidative electron transfer process (unlike the optical electron transition), acting as ancillary ligands that allow the transition between tetrahedral four-coordinated Cu(I) state to tetragonal five-coordinated Cu(II). Actually clear evidences of the entry of one solvent molecule in the inner coordination sphere of the complexes are proved by the Kolthoff and Lingane method. Proof of ionic couple formation is also found.
Heteroleptic Copper Photosensitizers: Why an Extended π-System Does Not Automatically Lead to Enhanced Hydrogen Production
Heberle, Martin,Tschierlei, Stefanie,Rockstroh, Nils,Ringenberg, Mark,Frey, Wolfgang,Junge, Henrik,Beller, Matthias,Lochbrunner, Stefan,Karnahl, Michael
, p. 312 - 319 (2017)
A series of heteroleptic copper(I) photosensitizers of the type [(P^P)Cu(N^N)]+with an extended π-system in the backbone of the diimine ligand has been prepared. The structures of all complexes are completely characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography. These novel photosensitizers were assessed with respect to the photocatalytic reduction of protons in the presence of triethylamine and [Fe3(CO)12]. Although the solid-state structures and computational results show no significant impact of the π-extension on the structural properties, decreased activities were observed. To explain this drop, a combination of electrochemical and photophysical measurements including time-resolved emission as well as transient absorption spectroscopy in the femto- to nanosecond time regime was used. Consequently, shortened excited state lifetimes caused by the rapid depopulation of the excited states located at the diimine ligand are identified as a major reason for the low photocatalytic performance.
Sulfonylation of Aryl Halides by Visible Light/Copper Catalysis
Cui, Wenwen,Jiang, Min,Lv, Jian,Song, Xiuyan,Sun, Kai,Xu, Guiyun,Yan, Qiuli,Yang, Daoshan
supporting information, p. 3663 - 3668 (2021/05/31)
An efficient visible-light-assisted, copper-catalyzed sulfonylation of aryl halides with sulfinates is reported. In our protocol, a single ligand CuI photocatalyst formed in situ was used in the photocatalytic transformation. Diverse organosulfones were obtained in moderate to good yields. This strategy demonstrates a promising approach toward the synthesis of diverse and useful organosulfones.
