Octahedral coordination of halide ions (I-, Br-, Cl-) sandwich bonded with tridentate mercuracarborand-3 receptors.
Octahedral coordination of halide ions (I-, Br-, Cl-) sandwich bonded with tridentate mercuracarborand-3 receptors.
复制标题
与三齿 Mercuracarborand-3 受体结合的卤离子（I-、Br-、Cl-）三明治的八面体配位。
DOI：
10.1021/ja010755l
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发表时间：
2001
影响因子：
15
通讯作者：
M. Hawthorne
中科院分区：
文献类型：
--
作者：
H. Lee;C. Knobler;M. Hawthorne
“反冠”B-六甲基9-汞碳硼烷-3（1）以eta（3）-夹心方式与卤离子（I-、Br-、Cl-）络合。填充的卤素离子p轨道和相应的空汞p轨道的对称性允许的相互作用导致三个等效的p（Hg）-p（卤素）-p（Hg）三中心两电子键和三明治结构。[Li.（H（2）O）（4）][1（2）.I].2CH（3）CN，MePPh3）[1（2）.Br].（（CH（3））（2）CO）（2）.（H（2）O）（2）和PPN[1（2）·Cl]的单晶X-射线衍射研究。化合物[Li.（H（2）O）（4）][1（2）.I].2CH（3）CN，以三斜晶系空间群P-1结晶，a = 13.312（8）A，B = 13.983（9）A，c = 13.996（9）A，α = 61.16（2）度，β = 82.34（2）度，γ = 86.58（2）度，V = 4365（2）A（3），Z = 1，R = 0.063，R（w）= 0.171。化合物MePPh（3）[1（2）.Br].（（CH（3））（2）CO）（2）.（H（2）O）（2）晶体属单斜晶系，空间群C2/c，a = 24.671（8）A，B = 17.576（6）A，c = 26.079（8）A，β = 106.424（6）度，V = 10847（6）A（3），Z = 8，R = 0.0607，R（w）= 0.1506。化合物PPN[1（2）.Cl]以单斜晶系空间群C2/m结晶，a = 37.27（2）A，B = 29.25（1）A，c = 10.990（4）A，β = 100.659（7）度，V = 11774（8）A（3），Z = 4，R = 0.0911，和R（w）= 0.2369。
The "anti-crown" B-hexamethyl 9-mercuracarborand-3 (1) was shown to complex halide ions (I-, Br-, Cl-) in an eta(3)-sandwich fashion. Symmetry-allowed interactions of the filled halide ion p-orbitals and the corresponding empty mercury p-orbitals result in three equivalent p(Hg)-p(halide)-p(Hg) three-center two-electron bonds and a sandwich structure. The molecular structures of [Li.(H(2)O)(4)][1(2).I].2CH(3)CN, MePPh(3)[1(2).Br].((CH(3))(2)CO)(2).(H(2)O)(2), and PPN[1(2).Cl] were determined by single-crystal X-ray diffraction studies. Compound [Li.(H(2)O)(4)][1(2).I].2CH(3)CN crystallized in the triclinic space group P-1, a = 13.312(8) A, b = 13.983(9) A, c = 13.996(9) A, alpha = 61.16(2) degrees, beta = 82.34(2) degrees, gamma = 86.58(2) degrees, V = 4365(2) A(3), Z = 1, R = 0.063, and R(w) = 0.171. Compound MePPh(3)[1(2).Br].((CH(3))(2)CO)(2).(H(2)O)(2) crystallized in the monoclinic space group C2/c, a = 24.671(8) A, b = 17.576(6) A, c = 26.079(8) A, beta = 106.424(6) degrees, V = 10847(6) A(3), Z = 8, R = 0.0607, and R(w) = 0.1506. Compound PPN[1(2).Cl] crystallized in the monoclinic space group C2/m, a = 37.27(2) A, b = 29.25(1) A, c = 10.990(4) A, beta = 100.659(7) degrees, V = 11774(8) A(3), Z = 4, R = 0.0911, and R(w) = 0.2369.