%0 Journal Article %1 Binder.1999 %A Binder, H. %A Kellner, R. %A Vaas, K. %A Hein, M. %A Baumann, F. %A Wanner, M. %A Kaim, W. %A Wedig, U. %A Honle, W. %A von Schering, H. G. %A Groeger, O. %A Engelhardt, G. %D 1999 %J Zeitschrift fuer Anorganische und Allgemeine Chemie %K NMR NMR;electronic borane bromide cluster cluster;nonaborane halo nonaborane prepn structure %N 10 %P 1638--1646 %R 10.1002/(SICI)1521-3749(199910)625:10\textless1638::AID-ZAAC1638\textgreater3.0.CO;2-V %T HB9X9 and H2B9X9 (X = Cl, Br, I): Neutral closo-nonaboranes in the novel series BnHn+1 and BnHn+2 syntheses, ab initio calculations, and electronic structures %V 625 %X Chem. redn. of B9X9 (X = Cl, Br, I) with gaseous HI proceeds stepwise to give the neutral paramagnetic clusters HB9X9., and the corresponding diamagnetic clusters H2B9X9. Together they comprise the 1st neutral derivs. in the series BnHn+1 and BnHn+2 with n = 9. The EPR spectra of the paramagnetic HB9X9. (X = Cl, Br, I) in glassy frozen CH2Cl2 solns. showed increasing g anisotropy for the heavier halogen derivs., illustrating significant halogen participation at the singly occupied MO due to the larger spin-orbit coupling contributions. Temp. dependent 1H NMR spectra of H2B9X9 (in CD3CN, X = Cl, Br) indicate H2B9X9, [HB9X9]-, and [CD3CNH]+ with H2B9X9 acting as a Bronsted acid. The corresponding 11B NMR spectra (in CD3CN) show the dianions [B9X9]2- as a result of the protonation of CD3CN. The 11B resonances of the species H2B9X9 and [HB9X9]- are obscured by superimposition of the two resonance lines of the dianions [B9X9]2-. Temp. dependent 11B[1H] MAS NMR spectra of H2B9Br9 show coalescence at 410 K and hence dynamic behavior of the neutral B9-cluster in the solid. Cyclic voltammetry expts. of H2B9Br9 in MeCN solvent are compatible with the redox sequence [B9Br9]2--[B9Br9].-B9Br9. Quantum chem. calcns. with the electron localization function (ELF) are described. [on SciFinder(R)]

@article{Binder.1999, abstract = {Chem. redn. of B9X9 (X = Cl, Br, I) with gaseous HI proceeds stepwise to give the neutral paramagnetic clusters HB9X9., and the corresponding diamagnetic clusters H2B9X9. Together they comprise the 1st neutral derivs. in the series BnHn+1 and BnHn+2 with n = 9. The EPR spectra of the paramagnetic HB9X9. (X = Cl, Br, I) in glassy frozen CH2Cl2 solns. showed increasing g anisotropy for the heavier halogen derivs., illustrating significant halogen participation at the singly occupied MO due to the larger spin-orbit coupling contributions. Temp. dependent 1H NMR spectra of H2B9X9 (in CD3CN, X = Cl, Br) indicate H2B9X9, [HB9X9]-, and [CD3CNH]+ with H2B9X9 acting as a Bronsted acid. The corresponding 11B NMR spectra (in CD3CN) show the dianions [B9X9]2- as a result of the protonation of CD3CN. The 11B resonances of the species H2B9X9 and [HB9X9]- are obscured by superimposition of the two resonance lines of the dianions [B9X9]2-. Temp. dependent 11B[1H] MAS NMR spectra of H2B9Br9 show coalescence at 410 K and hence dynamic behavior of the neutral B9-cluster in the solid. Cyclic voltammetry expts. of H2B9Br9 in MeCN solvent are compatible with the redox sequence [B9Br9]2--[B9Br9].-B9Br9. Quantum chem. calcns. with the electron localization function (ELF) are described. [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 Kaim, W. and Wedig, U. and Honle, W. and von Schering, H. G. and Groeger, O. and Engelhardt, G.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/21c0da83538268fa5ea2eeb13c088ecb5/b_schwederski}, doi = {10.1002/(SICI)1521-3749(199910)625:10{\textless}1638::AID-ZAAC1638{\textgreater}3.0.CO;2-V}, interhash = {2801d7285ed883130306fe440b7f0c11}, intrahash = {1c0da83538268fa5ea2eeb13c088ecb5}, issn = {0044-2313}, journal = {Zeitschrift fuer Anorganische und Allgemeine Chemie}, keywords = {NMR NMR;electronic borane bromide cluster cluster;nonaborane halo nonaborane prepn structure}, number = 10, pages = {1638--1646}, timestamp = {2019-07-15T11:42:10.000+0200}, title = {HB9X9 and H2B9X9 (X = Cl, Br, I): Neutral closo-nonaboranes in the novel series BnHn+1 and BnHn+2 syntheses, ab initio calculations, and electronic structures}, volume = 625, year = 1999 }