%0 Generic
%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
%T Chemistry of C-Trimethylsilyl-Substituted
Heterocarboranes. 30. Synthetic and Structural Studies
on Oxide Ion Encapsulating Tetralanthanide Tetrahedra
Surrounded by “Carbons Apart” C2B4-Carborane Ligands
(Ln(III) = La, Nd, Gd, Tb, Ho, Lu)
%U https://acs.figshare.com/articles/dataset/Chemistry_of_C_Trimethylsilyl_Substituted_Heterocarboranes_30_Synthetic_and_Structural_Studies_on_Oxide_Ion_Encapsulating_Tetralanthanide_Tetrahedra_Surrounded_by_Carbons_Apart_C_sub_2_sub_B_sub_4_sub_Carborane_Ligands_Ln_III_La_Nd_Gd_Tb_Ho_Lu_/3323839
%R 10.1021/om0496176.s004
%2 https://acs.figshare.com/ndownloader/files/5162623
%K molar ratios
%K lanthanacarboranes 3
%K 11 B NMR spectroscopy
%K R 2
%K 13 C
%K THF
%K C 2 B 3
%K η 5 fashion
%K Oxide Ion Encapsulating Tetralanthanide Tetrahedra
%K R 1
%K Structural Studies
%K holmium compound 6
%K oxide ion encapsulating tetralanthanide cores
%K Complexes 3
%K IR spectroscopy
%K LnCl 3
%K GOF
%K H 2 O
%K 1 H
%K diamagnetic compounds 2
%K 10.3 μ B
%K Carborane Ligands
%K lanthanide metal
%K species 3
%X The reactions of closo-exo-5,6-Na(THF)2-1-Na(THF)2-2,4-(SiMe3)2-2,4-C2B4H4 (1) with
anhydrous LnCl3 (Ln = La, Nd, Gd, Tb, Ho, Lu) and freshly distilled H2O in molar ratios of
5:4:1 gave crystalline solids, identified as the new oxolanthanacarboranes {[η5-1-Ln(THF)n-2,4-(SiMe3)2-2,4-C2B4H4]4(μ-Cl)2(μ4-O)}·yTHF (Ln = La (2), n = 0, y = 1; Ln = Nd (3), n = 1,
y = 0; Ln = Gd (4), n = 0, y = 1; Ln = Tb (5), n = 1, y = 0; Ln = Ho (6), n = 0, y = 1; Ln
= Lu (7), n = 1, y = 0), in 73−86% yields. All new compounds were characterized by IR
spectroscopy and elemental analyses. While the diamagnetic compounds 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 containing oxide ion encapsulating tetralanthanide cores,
Ln(μ4-O), that are stabilized by coordinating two carborane ligands: one in an η5 fashion
via the C2B3-bonding face and the other via two Ln−H−B bridges to a neighboring cage.
Complexes 3 and 5−7 crystallized in the monoclinic space group C2/c with a = 23.748(5),
23.577(5), 28.403(5), and 23.544(5) Å, b = 18.632(5), 18.513(5), 12.835(2), and 18.440(5) Å,
c = 22.798(5), 22.602(5), 27.879(5), and 22.480(5) Å, β = 104.338(5), 104.092(5), 117.820(3),
and 104.153(5)°, and V = 9774(64), 9568(4), 8989(13), and 9464(4) Å3, respectively (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,
respectively. The room-temperature magnetic susceptibility of the holmium compound 6 was
found to be 10.3 μB per lanthanide metal.
%I ACS Publications