%0 Journal Article %1 Binder.1999b %A Binder, H. %A Kellner, R. %A Vaas, K. %A Hein, M. %A Baumann, F. %A Wanner, M. %A Winter, R. %A Kaim, W. %A Honle, W. %A Grin, Y. %A Wedig, U. %A Schultheiss, M. %A Kremer, R. K. %A von Schnering, H. G. %A Groeger, O. %A Engelhardt, G. %D 1999 %J Zeitschrift fuer Anorganische und Allgemeine Chemie %K crystal haloborane;haloborane magnetism potential prepn redox structure %N 7 %P 1059--1072 %R 10.1002/(SICI)1521-3749(199907)625:7\textless1059::AID-ZAAC1059\textgreater3.0.CO;2-\# %T The closo-cluster triad. B9X9, B9X9.bul.-, and B9X92- with tricapped trigonal prisms (X = Cl, Br, I). Synthesis, crystal and electronic structures %V 625 %X Halogenation of nido-B10H14 with C2H2Cl4, C2Cl6, Br2, or I2, produces by cluster degrdn. the (2n)-closo-cluster B9X9 (X = Cl, Br, I). The synthesis of salts of the perhalogenated radical anions of the type (2n + 1)-closo-B9X9.bul.- and of the corresponding dianions (2n + 2)-closo-B9X92- from neutral B9X9 is described n is the no. of cluster atoms; (2n), (2n + 1), and (2n + 2) is the no. of cluster electrons. Mol. and crystal structures of B9Cl9, B9Br9, Ph4PB9Br9.CH2Cl2, and Bu4N2B9Br9.CH2Cl2 were detd. via x-ray diffraction. All 3 oxidn. states of the cluster retain the tricapped trigonal prism. The redn. of the clusters B9X9 was shown by cyclic voltammetry in CH2Cl2 to proceed via 2 successive 1-electron reversible steps, sepd. by at least 0.4 V. The paramagnetic radical anions B9X9.bul.- (X = Cl, Br) were further characterized by magnetic susceptibility measurements of Cp2FeB9X9 and Cp2CoB9X9, resp. The ESR spectra of B9X9.bul.- (X = Cl, Br, I) in glassy frozen CH2Cl2 solns. showed increasing g anisotropy for the heavier halogen derivs., illustrating significant halogen participation at the single occupied MO. The 11B NMR spectra of CD2Cl2 solns. of the neutral clusters B9X9 exhibit only 1 sharp resonance, indicating that the B atoms are highly fluxional in soln. In contrast, 2 different B resonances as expected for a rigid tricapped trigonal prism are clearly obsd. for the B9X92- dianions in solns. and for solid B9Br9 in the 11B MAS NMR spectra. Temp.-dependent 11B MAS NMR expts. on B9Br9 and B9Br92- in the solid state show a reversible coalescence of the 2 resonances at higher temp. 11B MAS NMR spectra and DTA measurements of B9Br92- showed a phase transition. on SciFinder(R)

@article{Binder.1999b, abstract = {Halogenation of nido-B10H14 with C2H2Cl4, C2Cl6, Br2, or I2, produces by cluster degrdn. the (2n)-closo-cluster B9X9 (X = Cl, Br, I). The synthesis of salts of the perhalogenated radical anions of the type (2n + 1)-closo-[B9X9].bul.- and of the corresponding dianions (2n + 2)-closo-[B9X9]2- from neutral B9X9 is described [n is the no. of cluster atoms; (2n), (2n + 1), and (2n + 2) is the no. of cluster electrons]. Mol. and crystal structures of B9Cl9, B9Br9, [Ph4P][B9Br9].CH2Cl2, and [Bu4N]2[B9Br9].CH2Cl2 were detd. via x-ray diffraction. All 3 oxidn. states of the cluster retain the tricapped trigonal prism. The redn. of the clusters B9X9 was shown by cyclic voltammetry in CH2Cl2 to proceed via 2 successive 1-electron reversible steps, sepd. by at least 0.4 V. The paramagnetic radical anions [B9X9].bul.- (X = Cl, Br) were further characterized by magnetic susceptibility measurements of [Cp2Fe][B9X9] and [Cp2Co][B9X9], resp. The ESR spectra of [B9X9].bul.- (X = Cl, Br, I) in glassy frozen CH2Cl2 solns. showed increasing g anisotropy for the heavier halogen derivs., illustrating significant halogen participation at the single occupied MO. The 11B NMR spectra of CD2Cl2 solns. of the neutral clusters B9X9 exhibit only 1 sharp resonance, indicating that the B atoms are highly fluxional in soln. In contrast, 2 different B resonances as expected for a rigid tricapped trigonal prism are clearly obsd. for the [B9X9]2- dianions in solns. and for solid B9Br9 in the 11B MAS NMR spectra. Temp.-dependent 11B MAS NMR expts. on B9Br9 and [B9Br9]2- in the solid state show a reversible coalescence of the 2 resonances at higher temp. 11B MAS NMR spectra and DTA measurements of [B9Br9]2- showed a phase transition. [on SciFinder(R)]}, added-at = {2019-07-15T13:41:23.000+0200}, author = {Binder, H. and Kellner, R. and Vaas, K. and Hein, M. and Baumann, F. and Wanner, M. and Winter, R. and Kaim, W. and Honle, W. and Grin, Y. and Wedig, U. and Schultheiss, M. and Kremer, R. K. and von Schnering, H. G. and Groeger, O. and Engelhardt, G.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/25a6ac3675651ebd803a00a623e4d9187/b_schwederski}, doi = {10.1002/(SICI)1521-3749(199907)625:7{\textless}1059::AID-ZAAC1059{\textgreater}3.0.CO;2-{\#}}, interhash = {70cc694486b20c6e0acb05ebc340fb26}, intrahash = {5a6ac3675651ebd803a00a623e4d9187}, issn = {0044-2313}, journal = {Zeitschrift fuer Anorganische und Allgemeine Chemie}, keywords = {crystal haloborane;haloborane magnetism potential prepn redox structure}, number = 7, pages = {1059--1072}, timestamp = {2019-07-15T11:42:10.000+0200}, title = {The closo-cluster triad. B9X9, [B9X9].bul.-, and [B9X9]2- with tricapped trigonal prisms (X = Cl, Br, I). Synthesis, crystal and electronic structures}, volume = 625, year = 1999 }