Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to 1,1'-Bis(diorganophosphino)ferrocenecopper(I)

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Organometallics, 33 (18): 4784--4791 (2014)
DOI: 10.1021/om500039a


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 prepd. and crystd. as BF4- or PF6- salts. Structure detns. of the tetrafluoroborates revealed asym. O4,N5 chelation of DML to copper(I) with longer Cu-O bonds of $\sim$2.25 \AA. Reversible oxidn. to 12+ and 22+ proceeds at the ferrocene units, while redn. 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 1-electron-redn. process is attributed to a two-species equil. caused by the hemilabile coordination of DML. Electrochem. and spectroelectrochem. measurements (UV-visible, IR) reveal increased coordination lability of the reduced complexes and their slow fragmentation. on SciFinder(R)



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