%0 Journal Article %1 Oki.1992 %A Oki, Aderemi R. %A Zhang, Hongming %A Maguire, John A. %A Hosmane, Narayan S. %A Ro, Hyekyeong %A Hatfield, William E. %A Moscherosch, Michael %A Kaim, Wolfgang. %D 1992 %J Organometallics %K Fenske Hall chromium crystal metallacarborane sandwich sandwich;MO sandwich;mol structure structure;magnetic susceptibility %N 12 %P 4202--4213 %R 10.1021/om00060a043 %T Chemistry of C-trimethylsilyl-substituted heterocarboranes. 10. Syntheses, structures, and properties of anionic chromium(III) and neutral chromium(IV) sandwiched metallacarborane complexes 1,1'-commo-Cr2-(SiMe3)-3-(R)-2,3-C2B4H42- and 1,1'-commo-Cr2,3-(SiMe3)2-2,3-C2B4H42 (R = SiMe3, Me, and H) %V 11 %X The reaction between CrCl3 and the THF-solvated double salt Na+Li+2-(SiMe3)-3-(R)-2,3-C2B4H42- (R = SiMe3, Me, H) in a molar ratio of 1:2 in benzene, followed by extn. and crystn. of the product from a soln. of benzene and THF or TMEDA, produces the sandwiched paramagnetic species Li(THF)41,1'-commo-Cr2,3-(SiMe3)2-2,3-C2B4H42 (I), Li(TMEDA)21,1'-commo-Cr2-(SiMe3)-3-Me)-2,3-C2B4H42 (II), and Li(TMEDA)21,1'-commo-Cr2-(SiMe3)-2,3-C2B4H52 (III) as bright red-orange and air-sensitive cryst. solids in 77, 45, and 64\% yields, resp. The structural assignments of I-III, which were made in part by IR spectra and FAB mass spectral anal., were confirmed by x-ray crystallog. The chromacarborane complexes are all ionic species in which the chromium metal is sandwiched by the two carborane ligands with the slight slippage of the metal toward the cage carbons. The crystal structures of complexes I and III were detd. Magnetic susceptibility and ESR spectra of I indicate the presence of high-spin Cr(III) complexes. The chem. oxidn. of I with PbCl2 produces the novel, diamagnetic, and neutral Cr(IV) sandwich complex 1,1'-commo-Cr2,3-(SiMe3)2-2,3-C2B4H42 (IV), as a dark-red, air-sensitive cryst. solid in 63\% yield. Compd. IV was characterized on the basis of 1H, 11B, and 13C NMR spectra, IR and mass spectra, magnetic susceptibility, and also by x-ray diffraction. on SciFinder(R)

@article{Oki.1992, abstract = {The reaction between CrCl3 and the THF-solvated double salt Na+Li+[2-(SiMe3)-3-(R)-2,3-C2B4H4]2- (R = SiMe3, Me, H) in a molar ratio of 1:2 in benzene, followed by extn. and crystn. of the product from a soln. of benzene and THF or TMEDA, produces the sandwiched paramagnetic species Li(THF)4[1,1'-commo-Cr[2,3-(SiMe3)2-2,3-C2B4H4]2] (I), Li(TMEDA)2[1,1'-commo-Cr[2-(SiMe3)-3-Me)-2,3-C2B4H4]2] (II), and Li(TMEDA)2[1,1'-commo-Cr[2-(SiMe3)-2,3-C2B4H5]2] (III) as bright red-orange and air-sensitive cryst. solids in 77, 45, and 64{\%} yields, resp. The structural assignments of I-III, which were made in part by IR spectra and FAB mass spectral anal., were confirmed by x-ray crystallog. The chromacarborane complexes are all ionic species in which the chromium metal is sandwiched by the two carborane ligands with the slight slippage of the metal toward the cage carbons. The crystal structures of complexes I and III were detd. Magnetic susceptibility and ESR spectra of I indicate the presence of high-spin Cr(III) complexes. The chem. oxidn. of I with PbCl2 produces the novel, diamagnetic, and neutral Cr(IV) sandwich complex 1,1'-commo-Cr[2,3-(SiMe3)2-2,3-C2B4H4]2 (IV), as a dark-red, air-sensitive cryst. solid in 63{\%} yield. Compd. IV was characterized on the basis of 1H, 11B, and 13C NMR spectra, IR and mass spectra, magnetic susceptibility, and also by x-ray diffraction. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Oki, Aderemi R. and Zhang, Hongming and Maguire, John A. and Hosmane, Narayan S. and Ro, Hyekyeong and Hatfield, William E. and Moscherosch, Michael and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/21848b0ef2c36c096ded0de281889085e/huebleriac}, doi = {10.1021/om00060a043}, interhash = {2085d3982bd1a913fb4590c9322d02e0}, intrahash = {1848b0ef2c36c096ded0de281889085e}, issn = {0276-7333}, journal = {Organometallics}, keywords = {Fenske Hall chromium crystal metallacarborane sandwich sandwich;MO sandwich;mol structure structure;magnetic susceptibility}, number = 12, pages = {4202--4213}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Chemistry of C-trimethylsilyl-substituted heterocarboranes. 10. Syntheses, structures, and properties of anionic chromium(III) and neutral chromium(IV) sandwiched metallacarborane complexes {1,1'-commo-Cr[2-(SiMe3)-3-(R)-2,3-C2B4H4]2}- and 1,1'-commo-Cr[2,3-(SiMe3)2-2,3-C2B4H4]2 (R = SiMe3, Me, and H)}, volume = 11, year = 1992 }