[9,9-(PMe2Ph)2-arachno-9,6-PtCB8H12] | 149610-55-9

• 英文名称: [9,9-(PMe2Ph)2-arachno-9,6-PtCB8H12]
• CAS: 149610-55-9
• 化学式: C₁₇H₃₄B₈P₂Pt
• 分子量: 581.972
• InChiKey: XLIYVIMERQLJPL-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：

  arachno-4-CB8H14 、 cis-[Me2Pt(PMe2Ph)2] 以 二氯甲烷 为溶剂， 以92%的产率得到[9,9-(PMe2Ph)2-arachno-9,6-PtCB8H12]
  参考文献：
  名称：

  Synthesis and Reactivity of 10-Vertex arachno-Platinacarboranes

  摘要：

  Reaction Of [Pt-3(CNR)(6)] with arachno-4-R'-4-CB8H13 in THF (tetrahydrofuran) gives the platina-monocarborane species [9,9-(CNR)2-6-R'-arachno-9,6-PtCB8H11] (R = Bu-t, R' = H (1); R = Xyl (C6H3Me2-2,6), R' = H (2); R = Bu-t, R' = Ph (3)). The related compound [9,9-(PMe2Ph)(2)-arachno-9,6-PtCB8H12] (5) can be synthesized by treating arachno-4-CB8H14 with [PtMe2(PMe2Ph)21 in CH2CL2 Compounds 1-3 and 5 are all formed in high yields (> 80%), enabling reactivity studies to be carried out. A single isocyanide ligand in 1 can be easily exchanged for a phosphine, as is the case with [9-CNBut-9-PPh3-arachno-9,6-PtCB8H12] (6), or, by using bidentate dppe (Ph2PCH2CH2PPh2), both isocyanide groups are replaced, giving [9,9-dppe-arachno-9,6-PtCB8H12] (7). Treatment with [NEt4][CN] allows the isocyanides in I to be replaced by cyanide ligands, giving the dianionic complex [NEt4](2)[9,9-(CN)(2)arachno-9,6-PtCB8H12] (8) or the monoanionic species [NEt4][9-CNBut-9-CN-arachno-9,6-PtCB8H12] (9) depending on the stoichiometry of the reaction. Reaction of I or 3 with 12 yields the platinum(IV) complexes [9,9-(CNBut)(2)-9,9-I-2-6-R'-arachno-9,6-PtCB8H11] (R' = H (10), Ph (11)), respectively, by an oxidative addition reaction. Using the same reagent, compound 7 forms solvent-dependent, boron-substituted products: [9,9-dppe-4,8-12-arachno-9,6-PtCB8H10] (12) is obtained in CH2Cl2, whereas [9,9dppe-4- {O(CH2)(4)I}-8-I-arachno-9,6-PtCB8H10] (13) results when THF is used as solvent.

  DOI：

  10.1021/om7012056

文献信息

• Eleven-vertex polyhedral monocarbaplatinaborane chemistry. Structure and fluxionality of [8,8-(PMe₂Ph)₂-nido-8,7-PtCB₉H₁₁]
  作者：Bohumil Štíbr、Tomáš Jelínek、John D. Kennedy、Xavier L. R. Fontaine、Mark Thornton-Pett

  DOI：10.1039/dt9930001261

  日期：——

  Reaction between [PtCl2(PMe2Ph)2] and [arachno-6-CB9H14]- in CH2Cl2 solution at room temperature yields yellow air-stable eleven-vertex [8,8-(PMe2Ph)2-nido-8,7-PtCB9H11] 1 (46-64%) together with small quantities of ten-vertex [9,9-(PMe2Ph)2-arachno-9,6-PtCB8H12] 2 (0-3%). Crystals of compound 1 are monoclinic, space group P2(1)/n, with a = 1186.8(1), b = 1554.1 (2), c = 1344.1(2) pm, beta = 95.02(1)-degrees and Z = 4. The structure refined to R, R' = 0.0297, 0.031 0 using 3938 data with I > 3sigma(I). The cluster structure is of the nido eleven-vertex type, with the platinum and carbon atoms occupying adjacent positions on the open face. There is some geometrical closure from pure nido, so that the gross cluster structure tends towards intermediacy between those of [7,7-(PMe2Ph)2-nido-7-PtB10H12] 4 and of the closo-structured species [1,1-(PMe2Ph)2-1,2,3-PtC2B8H10] 3. The NMR properties of 1 are reported and assessed for intermediacy between those of 3 and 4, and the analytical utility of NMR spectroscopy in assessing the metal-to-cluster bonding is developed by comparison with non-metallated species. The metal-to-carborane bonding sphere of compound 1 is fluxional, with DELTAG(double-dagger) ca. 62 kJ mol-1. The fluxional process involves an interconversion of enantiomers with the platinum centre and the bridging hydrogen atom migrating around the open face of the CB9H10} cage while the (PMe2Ph)2} exo polyhedral ligand sphere undergoes a half-twist.