[1,1,1-(PMe3)2H-arachno-(iridium)B8H8] | 82438-25-3

• 英文名称: [1,1,1-(PMe3)2H-arachno-(iridium)B8H8]
• 英文别名: nido-[1,1,1-H(PMe3)2(1-IrB8H8)]
• CAS: 82438-25-3
• 化学式: C₆H₂₇B₈IrP₂
• 分子量: 439.936
• InChiKey: QFFQSPYYLAHDPJ-CSPNZDHTSA-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：

  2-carbonyl-2,2-bis(trimethylphosphine)-nido-2-iridanonaborane 以 not given 为溶剂， 以<1的产率得到[1,1,1-(PMe3)2H-arachno-(iridium)B8H8]
  参考文献：
  名称：

  ：在metallaborane化学容易热诱导氧化簇蛛网膜→巢→闭合碳通过iridanonaboranes和iridadecaboranes，和铱的稳定表现出反应序列（V）氧化态

  摘要：

  具有相邻开放桥连氢原子和末端Ir–H原子的Iridanonaboranes和iridadecaboranes在涉及稳定可分离铱（V）物种的正式簇氧化中很容易损失H 2。

  DOI：

  10.1039/c39820000346

文献信息

• Nine-vertex metallaborane chemistry. Preparation and characterisation of [1,1,1-(PMe3)2H-isocloso-IrB8H7-8-X], where X = H or Cl
  作者：Jonathan Bould、Ross W. Harrington、William Clegg、John D. Kennedy

  DOI：10.1016/j.jorganchem.2012.08.012

  日期：2012.12

  The heating of solutions of [(CO)(PMe3)(2)H-arachno-IrB8H11Cl] 1a or [(CO)(PMe3)(2)-nido-IrB8H10Cl] 2 in xylene results in the iridanonaborane cluster compound [1,1,1-(PMe3)(2)H-isocloso-IrB8H7-8-Cl] 3a in yields of up to 42%. Significantly less stable is the non-chlorinated analogue [1,1,1-(PMe3)(2)H-isocloso-IrB8H8] 3b, prepared via solutions of [(CO)(PMe3)(2)H-arachno-IrB8H12] 1b and excess nido-B10H14 in refluxing xylene. The structures of the IrB8} units of 3a and 3b, characterised by multielement NMR spectroscopy and by single-crystal X-ray diffraction analyses, both approximate closely to an idealised C-2v symmetry with the IrH(PMe3)(2)} moiety capping the six-membered open faces of arachno/nido-shaped B-8} units. This structural geometry differs significantly from the classical nine-vertex closo D-3h tricapped trigonal prismatic (ttp) structure of the [closo-B9H9](2-) anion. NMR spectroscopy shows that both 3a and 3b are fluxional with regard to the orientation of the Ir(H(PMe3)} ligand set relative to the IrB8} unit. Density functional theory (DFT) calculations have been carried out to help rationalise and extend the conclusions from the experimental observations. The calculations suggest that the isocloso cluster structure for chloro-substituted 3a may be both the kinetically and the thermodynamically favoured one, whereas for unsubstituted 3b a ttp structure would be thermodynamically the more stable and so the observed isocloso structure may well be the favoured kinetic product. However, the differences in these relative stabilities are marginal, and both compounds are unstable in solution relative to a general decomposition, 3b much more so than 3a, so there may be little significance in the relative stabilities of the ttp structures: the calculations suggest that the energy barrier to an isocloso-to-ttp conversion would preclude a decomposition pathway for 3a or 3b via a ttp structure at room temperature. (C) 2012 Elsevier B. V. All rights reserved.