%0 Journal Article %1 Wang.2004 %A Wang, Jianhui %A Li, Shoujian %A Zheng, Chong %A Li, Ang %A Hosmane, Narayan S. %A Maguire, John A. %A Roesky, Herbert W. %A Cummins, Christopher C. %A Kaim, Wolfgang. %D 2004 %J Organometallics %K bridged carborane complex dicarbahexaborane lanthanide oxo prepn prepn;crystal prepn;mol structure tetramer %N 20 %P 4621--4629 %R 10.1021/om0496176 %T Chemistry of C-Trimethylsilyl-Substituted Heterocarboranes. 30. Synthetic and Structural Studies on Oxide Ion Encapsulating Tetralanthanide Tetrahedra Surrounded by \dqCarbons Apart\dq C2B4-Carborane Ligands (Ln(III) = La, Nd, Gd, Tb, Ho, Lu) %V 23 %X Tetrameric m4-oxo-bridged lanthanadicarbaheptaboranes were prepd. and characterized. The reactions of closo-exo-5,6-Na(THF)2-1-Na(THF)2-2,4-(SiMe3)2-2,4-C2B4H4 (1) with anhyd. LnCl3 (Ln = La, Nd, Gd, Tb, Ho, Lu) and freshly distd. H2O in molar ratios of 5:4:1 gave cryst. solids, identified as the new oxolanthanacarboranes h5-1-Ln(THF)n-2,4-(SiMe3)2-2,4-C2B4H44(m-Cl)2(m4-O)·yTHF (y = 0, 1; 2 Ln = La, n = 0; 3 Ln = Nd, n = 1; 4 Ln = Gd, n = 0; 5 Ln = Tb, n = 1; 6 Ln = Ho, n = 0; 7 Ln = Lu, n = 1), in 73-86\% yields. All new compds. were characterized by IR spectroscopy and elemental analyses. While the diamagnetic compds. 2 and 7 were also studied by 1H, 13C, and 11B NMR spectroscopy, the lanthanacarboranes 3 and 5-7 were further characterized by single-crystal x-ray diffraction analyses. The species 3, 5, and 7 were found to be isostructural, all contg. oxide ion encapsulating tetralanthanide cores, Ln(m4-O), that are stabilized by coordinating two carborane ligands: one in an h5 fashion via the C2B3-bonding face and the other via two Ln-H-B bridges to a neighboring cage. Complexes 3 and 5-7 crystd. in the monoclinic space group C2/c with a = 23.748(5), 23.577(5), 28.403(5), and 23.544(5) \AA, b = 18.632(5), 18.513(5), 12.835(2), and 18.440(5) \AA, c = 22.798(5), 22.602(5), 27.879(5), and 22.480(5) \AA, b = 104.338(5), 104.092(5), 117.820(3), and 104.153(5)°, and V = 9774(64), 9568(4), 8989(13), and 9464(4) \AA3, resp. (Z = 4). The final refinements of 3 and 5-7 converged at R1 = 0.0795, 0.0703, 0.0367, and 0.0904; wR2 =0.1793, 0.1686, 0.794, and 0.1844, and GOF = 1.401, 1.305, 1.446, and 1.498, resp. The room-temp. magnetic susceptibility of the holmium compd. 6 was found to be 10.3 mB per lanthanide metal. on SciFinder(R)

@article{Wang.2004, abstract = {Tetrameric \textgreek{m}4-oxo-bridged lanthanadicarbaheptaboranes were prepd. and characterized. The reactions of closo-exo-5,6-Na(THF)2-1-Na(THF)2-2,4-(SiMe3)2-2,4-C2B4H4 (1) with anhyd. LnCl3 (Ln = La, Nd, Gd, Tb, Ho, Lu) and freshly distd. H2O in molar ratios of 5:4:1 gave cryst. solids, identified as the new oxolanthanacarboranes [[\textgreek{h}5-1-Ln(THF)n-2,4-(SiMe3)2-2,4-C2B4H4]4(\textgreek{m}-Cl)2(\textgreek{m}4-O)]·yTHF (y = 0, 1; 2 Ln = La, n = 0; 3 Ln = Nd, n = 1; 4 Ln = Gd, n = 0; 5 Ln = Tb, n = 1; 6 Ln = Ho, n = 0; 7 Ln = Lu, n = 1), in 73-86{\%} yields. All new compds. were characterized by IR spectroscopy and elemental analyses. While the diamagnetic compds. 2 and 7 were also studied by 1H, 13C, and 11B NMR spectroscopy, the lanthanacarboranes 3 and 5-7 were further characterized by single-crystal x-ray diffraction analyses. The species 3, 5, and 7 were found to be isostructural, all contg. oxide ion encapsulating tetralanthanide cores, Ln(\textgreek{m}4-O), that are stabilized by coordinating two carborane ligands: one in an \textgreek{h}5 fashion via the C2B3-bonding face and the other via two Ln-H-B bridges to a neighboring cage. Complexes 3 and 5-7 crystd. in the monoclinic space group C2/c with a = 23.748(5), 23.577(5), 28.403(5), and 23.544(5) {\AA}, b = 18.632(5), 18.513(5), 12.835(2), and 18.440(5) {\AA}, c = 22.798(5), 22.602(5), 27.879(5), and 22.480(5) {\AA}, \textgreek{b} = 104.338(5), 104.092(5), 117.820(3), and 104.153(5)°, and V = 9774(64), 9568(4), 8989(13), and 9464(4) {\AA}3, resp. (Z = 4). The final refinements of 3 and 5-7 converged at R1 = 0.0795, 0.0703, 0.0367, and 0.0904; wR2 =0.1793, 0.1686, 0.794, and 0.1844, and GOF = 1.401, 1.305, 1.446, and 1.498, resp. The room-temp. magnetic susceptibility of the holmium compd. 6 was found to be 10.3 \textgreek{m}B per lanthanide metal. [on SciFinder(R)]}, added-at = {2019-07-15T13:41:23.000+0200}, author = {Wang, Jianhui and Li, Shoujian and Zheng, Chong and Li, Ang and Hosmane, Narayan S. and Maguire, John A. and Roesky, Herbert W. and Cummins, Christopher C. and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/24e8856a367a74c1427382a3f7817ccdc/b_schwederski}, doi = {10.1021/om0496176}, interhash = {b6c9ce601ed1614dfd0332db235d2430}, intrahash = {4e8856a367a74c1427382a3f7817ccdc}, issn = {0276-7333}, journal = {Organometallics}, keywords = {bridged carborane complex dicarbahexaborane lanthanide oxo prepn prepn;crystal prepn;mol structure tetramer}, number = 20, pages = {4621--4629}, timestamp = {2019-07-15T11:42:10.000+0200}, title = {Chemistry of C-Trimethylsilyl-Substituted Heterocarboranes. 30. Synthetic and Structural Studies on Oxide Ion Encapsulating Tetralanthanide Tetrahedra Surrounded by {\dq}Carbons Apart{\dq} C2B4-Carborane Ligands (Ln(III) = La, Nd, Gd, Tb, Ho, Lu)}, volume = 23, year = 2004 }