%0 Journal Article %1 Jana.2014 %A Jana, Rajkumar %A Sarkar, Biprajit %A Strobel, Sabine %A Mobin, Shaikh M. %A Kaim, Wolfgang %A Fiedler, Jan. %D 2014 %J Organometallics %K complex copper diphosphinoferrocene electrochem;crystal lumazine prepn structure %N 18 %P 4784--4791 %R 10.1021/om500039a %T Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1'-Bis(diorganophosphino)ferrocene]copper(I) %V 33 %X [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 [1]2+ and [2]2+ 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)]

@article{Jana.2014, abstract = {[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 [1]2+ and [2]2+ 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)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Jana, Rajkumar and Sarkar, Biprajit and Strobel, Sabine and Mobin, Shaikh M. and Kaim, Wolfgang and Fiedler, Jan.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/27616634f059a0a6eb3207fce1e97b1bc/huebleriac}, doi = {10.1021/om500039a}, interhash = {145e1cf9b8bc056143fb0719c8e2af77}, intrahash = {7616634f059a0a6eb3207fce1e97b1bc}, issn = {0276-7333}, journal = {Organometallics}, keywords = {complex copper diphosphinoferrocene electrochem;crystal lumazine prepn structure}, number = 18, pages = {4784--4791}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1'-Bis(diorganophosphino)ferrocene]copper(I)}, volume = 33, year = 2014 }