Add time:07/16/2019         Source:sciencedirect.com

The formation of mixed-valence copper complexes with dialkyl sulfides or triphenylphosphine in the catalytic isomerization of DICHLOROBUTENE (cas 11069-19-5)s was investigated kinetically and spectroscopically (UV–Vis, IR, EPR, NMR). These species were prepared both starting from Cu(I) and Cu(II) compounds. The complexes containing 3 or 4 copper ions in different oxidation states, substrate and donor molecules were found to play a key role in catalysis. Chlorolefins with allylic chlorine atom may stabilize mixed-valence complexes as bridging ligand between Cu(I) and Cu(II). The EPR spectra of these complexes provide the five-coordinated Cu(II) with a trigonal–bipiramydal geometry of coordination sphere. The simultaneous presence of Cu(I) and Cu(II) in polynuclear structure is proposed to favor the electron transfer step in the reaction mechanism.

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