Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I)

0434726 - ÚFCH JH 2015 RIV US eng J - Článek v odborném periodiku
Jana, R. - Sarkar, B. - Strobel, S. - Mobin, S. M. - Kaim, W. - Fiedler, Jan
Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I).
Organometallics. Roč. 33, č. 18 (2014), s. 4784-4791. ISSN 0276-7333. E-ISSN 1520-6041
Grant CEP: GA MŠMT LD14129
Institucionální podpora: RVO:61388955
Klíčová slova: electrochemistry * metal complexes * crystal structure
Kód oboru RIV: CG - Elektrochemie
Impakt faktor: 4.126, rok: 2014

The complex cations [Cu(dippf)(DML)](+) ([1](+)) and [Cu(dppf)(DML)](+) ([2](+)), where dippf = 1,1'-bis(diisopropylphosphino)ferrocene, dppf = 1,1'-bis(diphenylphosphino)ferrocene, and DML = 1,3-dimethyllumazine, were prepared and crystallized as BF4- or PF6- salts. Structure determinations of the tetrafluoroborates revealed asymmetric O-4,N-5 chelation of DML to copper(I) with longer Cu-O bonds of about 2.25 angstrom. Reversible oxidation to [1](2+) and [2](2+) proceeds at the ferrocene units, while reduction leads to the neutral radical complexes [1] and [2] with the unpaired electron localized on the DML ligand. The occurrence of two voltammetric steps for the one-electron-reduction process is attributed to a two-species equilibrium caused by the hemilabile coordination of DML. Electrochemical and spectroelectrochemical measurements (UV-vis, IR) reveal increased coordination lability of the reduced complexes and their slow fragmentation.
Trvalý link: http://hdl.handle.net/11104/0238723