%0 Journal Article %1 Lorenzen.1998 %A Lorenzen, Volker %A Preetz, Wilhelm %A Baumann, Frank %A Kaim, Wolfgang. %D 1998 %J Inorganic Chemistry %K ESR;radical cluster cluster;Raman cluster;magnetic cluster;perhalogenated dianionic electrochem hexaborate monoanionic oxidn perhalogenated prepn property stabilization %N 16 %P 4011--4014 %R 10.1021/IC9802698 %T Paramagnetic Cluster Ions [B6HalnHal'6-n].bul.- (Hal, Hal' = Cl, Br, I). EPR Evidence for Radical Stabilization through Electronic Effects of the Halogen Substituents %V 37 %X Monoanionic hexaborate cluster radicals [B6HalnHal'6-n].bul.- with mixed halogen substitution were prepd. from oxidizable dianionic precursors and were characterized by vibrational and UV-visible spectroscopy. EPR studies of these and the structurally established homoleptic species [B6Hal6].bul.- (Hal = Cl, Br, I) reveal strongly increasing g anisotropy and relaxation rate on replacing Cl by Br and esp. I substituents; the very stable B6I6.bul.- ion (g1 = 2.04, g2 = 1.66, g3 = 1.15) thus exhibits an EPR spectrum only at 4 K. The extent of these effects is attributed to the Jahn-Teller situation in [B6X6].bul.- with only partial occupancy of a degenerate MO. Both the absence of B-H bonds and the evidently strong participation of the halogen substituents in the singly occupied MO contribute to the extraordinary stability of these cluster radicals. [on SciFinder(R)]

@article{Lorenzen.1998, abstract = {Monoanionic hexaborate cluster radicals [B6HalnHal'6-n].bul.- with mixed halogen substitution were prepd. from oxidizable dianionic precursors and were characterized by vibrational and UV-visible spectroscopy. EPR studies of these and the structurally established homoleptic species [B6Hal6].bul.- (Hal = Cl, Br, I) reveal strongly increasing g anisotropy and relaxation rate on replacing Cl by Br and esp. I substituents; the very stable B6I6.bul.- ion (g1 = 2.04, g2 = 1.66, g3 = 1.15) thus exhibits an EPR spectrum only at 4 K. The extent of these effects is attributed to the Jahn-Teller situation in [B6X6].bul.- with only partial occupancy of a degenerate MO. Both the absence of B-H bonds and the evidently strong participation of the halogen substituents in the singly occupied MO contribute to the extraordinary stability of these cluster radicals. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Lorenzen, Volker and Preetz, Wilhelm and Baumann, Frank and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/22f1f08e3a9b5c7fe5ef2f269d92fb22c/huebleriac}, doi = {10.1021/IC9802698}, interhash = {16bd4f3fd8a973bb3cb496b9846146c1}, intrahash = {2f1f08e3a9b5c7fe5ef2f269d92fb22c}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {ESR;radical cluster cluster;Raman cluster;magnetic cluster;perhalogenated dianionic electrochem hexaborate monoanionic oxidn perhalogenated prepn property stabilization}, number = 16, pages = {4011--4014}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Paramagnetic Cluster Ions [B6HalnHal'6-n].bul.- (Hal, Hal' = Cl, Br, I). EPR Evidence for Radical Stabilization through Electronic Effects of the Halogen Substituents}, volume = 37, year = 1998 }