[K(crypt 2.2.2)][Ta(C2Si(C4H9)3)6] | 214756-52-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [K(crypt 2.2.2)][Ta(C2Si(C4H9)3)6]
• CAS: 214756-52-2
• 化学式: C₁₈H₃₆N₂O₆*C₈₄H₁₆₂Si₆Ta*K
• 分子量: 1937.26
• InChiKey: HDLBGDPHTIKUAC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  、 4,7,13,16,21,24-六氧-1,10-二氮双环[8.8.8]二十六烷 以 四氢呋喃 为溶剂， 生成 [K(crypt 2.2.2)][Ta(C2Si(C4H9)3)6]
  参考文献：
  名称：

  Structural Dichotomy in Six-Coordinate d⁰ Complexes:  Trigonal Prismatic (^tBu₃SiC⋮C)₆Ta^- and Octahedral (^tBu₃SiC⋮C)₆M^2- (M = Zr, Hf)

  摘要：

  Utilization of the bulky acetylide, (Bu3SiC)-Bu-t=C-, enabled the synthesis of several early metal polyacetylides. Addition of NaC=CH to (Bu3SiBr)-Bu-t in dimethyl sulfoxide afforded (Bu3SiC)-Bu-t=CH, which was deprotonated to yield (Bu3SiC)-Bu-t=CLi. Treatment of ZrCl4, HfCl4, and TaCl5 with varying amounts of Bu-t(3)-SiC=CLi gave {(THF)(2)Li((Bu3SiC)-Bu-t=C)(2)}Zr(C=(CSiBu3)-Bu-t)(3)(THF) (1; THF = tetrahydrofuran), {(Et2O)Li(Bu-t(3)-SiC=C)(2)}Hf(C=(CSiBu3)-Bu-t)(3)(OEt2) (2), {Li((Bu3SiC)-Bu-t=C)(3)}(2)M (M = Zr, 6; Hf,7), and {Li((Bu3SiC)-Bu-t=C)(3)}Ta(C=(CSiBu3)-Bu-t)(3) (3). Metathesis of 3 with KOTf generated KTa(C=(CSiBu3)-Bu-t)(6) (4) and cation sequestration of 4 with crypt 2.2.2 provided [K(crypt 2.2.2)][Ta(C=(CSiBu3)-Bu-t)(6)] (5). Single-crystal X-ray structural studies determined the structures (core symmetry) of 1 (O-h), 2, (O-h), 3 (D-3), 5 (D-3), 6 (O-h), and 7 (O-h). The D-3h to D-3 twist in 3 and 5 has a steric origin, and the counterion position appears inconsequential. Origins of the structural preferences illustrated by the dichotomous twisted trigonal prismatic and octahedral cores of the d(0) hexaacetylides 5 and 6 were probed through density functional (ADF) and effective core potential (GAMESS) calculations. The structural difference results from a lessening electronic preference for the trigonal prism-primarily a greater HOMO/LUMO gap-upon moving from Ta to Zr, minor steric factors, and increased interligand repulsions in the dianion (VSEPR).

  DOI：

  10.1021/ja9802899