Synthesis, Electronic Spectra and Solvent-Induced Reversible Dissociation of Diphosphine(hexafluoroacetylacetonato)copper(I) Complexes
2014
Pawlowski, Valeri | Strasser, Andreas | Vogler, A. (Arnd)
The complexes Cuᴵ(P-P)(hfac) with P-P = 1,2-bis(diphenylphosphino)ethane (diphos), 1,3-bis-(diphenylphosphino)propane (prophos), 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl (binap) and hfac = hexafluoroacetylacetonate were synthesized and spectroscopically characterized. In the solid state or in solutions of non-polar solvents these compounds are yellow owing to a long-wavelength (hfac⁻ →P-P) ligand-to-ligand charge transfer absorption. In coordinating solvents such as CH₃CN the complexes undergo a reversible dissociation according to the equation: Cu(P-P)(hfac) + n CH₃CN ⇌ [Cu(P-P)(CH₃CN)ₙ]⁺hfac⁻.While the complexes are not luminescent the ion pairs [Cu(P-P)(CH₃CN)ₙ]⁺hfac⁻ are emissive at 77 K. The cations and the anions show separate emissions as indicated by the excitation spectra.
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