Diselenophosphate-Induced Conversion of an Achiral [Cu20H11{S2P(OiPr)2}9] into a Chiral [Cu20H11{Se2P(OiPr)2}9] Polyhydrido Nanocluster
Diselenophosphate-Induced Conversion of an Achiral [Cu20H11{S2P(OiPr)2}9] into a Chiral [Cu20H11{Se2P(OiPr)2}9] Polyhydrido Nanocluster
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DOI：
10.1002/anie.201506736
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发表时间：
2015-11-09
影响因子：
16.6
通讯作者：
Liu, C. W.
中科院分区：
文献类型：
--
作者：
Dhayal, Rajendra S.;Liao, Jian-Hong;Liu, C. W.
采用配体交换法，以非手性的[Cu 20 H11 {S2 P（OiPr）（2）}（9）]（1（H））为原料，合成了一种具有C-3对称性的多手性铜纳米簇[Cu 20 H11 {Se 2 P（OiPr）（2）}（9）]（2（H））.该结构具有扭曲的立方八面体Cu-13核，其中两个三角形面沿C-3轴被沿着覆盖，一个被Cu-6冲天炉覆盖，另一个被单个Cu原子覆盖。Cu-20骨架被9个二硒磷酸和11个氢化物配体进一步稳定。2（H）的多核NMR谱中氢化物、磷和硒共振的数目及其分裂模式表明手性Cu 20 H 11核在溶液中保持其C-3对称性。通过中子衍射实验定位了11个氢化物配体，并显示为帽状（3）-H和间隙（5）-H配体（在方锥和三角双锥腔中），作为简化模型的DFT计算支持[Cu 20 H 11（Se 2 PH 2）（9）]（2（H））。
A polyhydrido copper nanocluster, [Cu20H11{Se2P(OiPr)(2)}(9)] (2(H)), which exhibits an intrinsically chiral inorganic core of C-3 symmetry, was synthesized from achiral [Cu20H11{S2P(OiPr)(2)}(9)] (1(H)) of C-3h symmetry by a ligand-exchange method. The structure has a distorted cuboctahedral Cu-13 core, two triangular faces of which are capped along the C-3 axis, one by a Cu-6 cupola and the other by a single Cu atom. The Cu-20 framework is further stabilized by 9 diselenophosphate and 11 hydride ligands. The number of hydride, phosphorus, and selenium resonances and their splitting patterns in multinuclear NMR spectra of 2(H) indicate that the chiral Cu20H11 core retains its C-3 symmetry in solution. The 11 hydride ligands were located by neutron diffraction experiments and shown to be capping (3)-H and interstitial (5)-H ligands (in square-pyramidal and trigonal-bipyramidal cavities), as supported by DFT calculations on [Cu20H11(Se2PH2)(9)] (2(H)) as a simplified model.