carbonylchloro[cis,cis-1,3,5-tris(diphenylphosphino)cyclohexane]iridium(I) | 157044-35-4

• 英文名称: carbonylchloro[cis,cis-1,3,5-tris(diphenylphosphino)cyclohexane]iridium(I)
• CAS: 157044-35-4
• 化学式: C₄₃H₃₉ClIrOP₃
• 分子量: 892.376
• InChiKey: KATJLQNVTQKZEH-UHFFFAOYSA-M

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

• 作为反应物：
  描述：

  carbonylchloro[cis,cis-1,3,5-tris(diphenylphosphino)cyclohexane]iridium(I) 在 Cl₂ 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到trichloro[cis,cis-1,3,5-tris(diphenylphosphino)cyclohexane]iridium(III)
  参考文献：
  名称：

  cis,cis-1,3,5-Tris(diphenylphosphino)cyclohexane (tdppcy). A new tripodal phosphine that forms metal complexes with adamantane-type structures. rystal structure of Ir(tdppcy)Cl3

  摘要：

  The novel tridentate phosphine cis,cis-1,3,5-tris(diphenylphosphino)cyclohexane (tdppcy) (3) has been synthesized. Treatment of tdppcy with Mo(C7H8)(CO)3 and lr(PPh3)2(CO)CI yields octahedral Mo(tdppcy)(CO)3 (4) and trigonal-bipyramidal Ir(tdppcy)(CO)Cl.(5), respectively. Compound S is transformed into either Ir(tdppcy)(CO)H (6) or lr(tdppcy)(CO)(H)2+ (7) by treatment with NaBH4 in refluxing THF. Complex 5 can be oxidized by dichloromethane or Cl2 to the trichloro complex lr(tdppcy)Cl3 (8), which can be converted into the dihydride Ir(tdppcy)(H)2Cl (9) by treatment with NaBH4 in THF. The dynamic behavior of the highly fluxional pentacoordinate complexes 5 and 6 has been studied by VT P-31{H-1} NMR spectroscopy. An X-ray diffraction study has been carried out on 8 . 3CH2Cl2.

  DOI：

  10.1016/0022-328x(94)80221-1
• 作为产物：
  描述：

  cis,cis-1,3,5-tris-(diphenylphosphino)cyclohexane 、 bis(triphenylphosphine)carbonyliridium(I) chloride 以 甲苯 为溶剂， 以96%的产率得到carbonylchloro[cis,cis-1,3,5-tris(diphenylphosphino)cyclohexane]iridium(I)
  参考文献：
  名称：

  cis,cis-1,3,5-Tris(diphenylphosphino)cyclohexane (tdppcy). A new tripodal phosphine that forms metal complexes with adamantane-type structures. rystal structure of Ir(tdppcy)Cl3

  摘要：

  The novel tridentate phosphine cis,cis-1,3,5-tris(diphenylphosphino)cyclohexane (tdppcy) (3) has been synthesized. Treatment of tdppcy with Mo(C7H8)(CO)3 and lr(PPh3)2(CO)CI yields octahedral Mo(tdppcy)(CO)3 (4) and trigonal-bipyramidal Ir(tdppcy)(CO)Cl.(5), respectively. Compound S is transformed into either Ir(tdppcy)(CO)H (6) or lr(tdppcy)(CO)(H)2+ (7) by treatment with NaBH4 in refluxing THF. Complex 5 can be oxidized by dichloromethane or Cl2 to the trichloro complex lr(tdppcy)Cl3 (8), which can be converted into the dihydride Ir(tdppcy)(H)2Cl (9) by treatment with NaBH4 in THF. The dynamic behavior of the highly fluxional pentacoordinate complexes 5 and 6 has been studied by VT P-31{H-1} NMR spectroscopy. An X-ray diffraction study has been carried out on 8 . 3CH2Cl2.

  DOI：

  10.1016/0022-328x(94)80221-1

文献信息

• Stereochemical and Electronic Control of Functionalized Tripodal Phosphines. Reactivity of the Adamantane-Type Ir(tripod)(CO)Cl (tripod = <i>cis,cis</i>-1,3,5-(PPh₂)₃-1,3,5-X₃C₆H₆; X = H, COOMe, CN) Complexes toward H⁺, H₂, CO, and C₂H₄¹
  作者：Philipp Stössel、Wolfgang Heins、Hermann A. Mayer、Riad Fawzi、Manfred Steimann

  DOI：10.1021/om960006q

  日期：1996.7.23

  conditions a phosphine arm dissociates from 2a to form the dihydride Ir(η2-tdppcyme)(CO)(H)2Cl (2c‘). In a CO atmosphere the Ir(tripod)(CO)Cl (1a−3a) complexes give the dicarbonyl derivatives [Ir(tripod)(CO)2]Cl (1d‘−3d‘). The dicarbonyls 2d‘ and 3d‘ are in an equilibrium with their starting materials. Replacement of the Cl- by BPh4- allows the isolation of all three dicarbonyl complexes. Treatment of

  用Ir（PPh 3）2（CO）Cl处理三脚架膦配体顺式，顺式-1,3,5-三（二苯基膦基）-1,3,5-三（甲氧基羰基）环己烷（tdppcyme）（2）得到羰基氯络合物Ir（tdppcyme）（CO）Cl（2a）。NMR光谱研究证明，在具有两个和三个分别与铱配位的膦基的方平面（2a '）和三角双锥体（2a）络合物之间存在动态平衡。这与类似的配合物Ir（三脚架）（CO）Cl（1a，3a）[三脚架=顺式，顺式-1,3,5-三（二苯基膦基）环己烷（tdppcy）（1），顺式，顺式-1,3,5-三氰基顺式，顺-1,3,5-三（二苯基膦基）环己烷（tdppcycn）（3）]仅以三角-双锥体形式存在。仅在配体主链的功能上不同的三种化合物Ir（三脚架）（CO）Cl（1a - 3a）显示出改变的碱性，因此反应模式也不同。羰基氯配合物1a - 3a容易被强酸HBF 4质子化，得到八面体阳离子1b - 3b。弱酸NH