cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(methoxycarbonyl)cyclohexane | 165059-15-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(methoxycarbonyl)cyclohexane
• CAS: 165059-15-4
• 化学式: C₄₈H₄₅O₆P₃
• 分子量: 810.803
• InChiKey: QWMQZEXEMSDRNB-ALJGMXIHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  57.0
• 可旋转键数：
  12.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  78.9
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(methoxycarbonyl)cyclohexane 、 nickel dichloride 以 四氢呋喃 为溶剂， 以88%的产率得到cis-dichloro[η(2)-cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris-(methoxycarbonyl)cyclohexane]nickel(II)
  参考文献：
  名称：

  官能化三脚架膦配体的Ni-，Pd-和Pt配合物的合成与表征

  摘要：

  三环醚，酯和氰基官能化的膦配体（tdppcymome）（a），（tdppcyme）（b）和（tdppcycn）（c）分别为环己烷骨架类型cis，cis -1,3,5-（ PPh 2）3 -1,3,5-（R）3 -C 6 H 5（tdppcyR）（R = -CH 2 OCH 3，-COOCH 3和-CN）分别用环辛二烯配合物M（COD）处理）氯2（1，2）（M =铂，钯）和的NiCl 2（3）。潜在的三齿配体形成具有这些过渡金属的四配位，二齿二氯络合物顺-M II（η 2 -tdppcyR）氯2（1A - Ç，2A - Ç，图3a - Ç），其中，两个二苯基膦基供体基团键合到金属中心，一种磷保持不配位。双金属铂锡配合物顺式-Pt（tdppcyme）Cl（SnCl 3）（1e）处理SnCl 2醚官能化配合物1b）。进行了详细的NMR研究以表征结构性质。铂和钯配合物具有正方形平面的配位几何形状，

  DOI：

  10.1016/s0022-328x(99)00331-9
• 作为产物：
  描述：

  TRIMETHYL CIS,CIS-1,3,5-CYCLOHEXANETRICARBOXYLATE 、 二苯基氯化膦 在 lithium diisopropyl amide 作用下， 生成 cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(methoxycarbonyl)cyclohexane
  参考文献：
  名称：

  Synthesis and X-ray molecular structure of cis, cis-1,3,5-Tris(diphenylphosphino)- 1,3,5-tris(methoxycarbonyl) cyclohexane

  摘要：

  The novel tripodal phosphine ligand cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(methoxycarbonyl)cyclohexane(tdppcyme) (tdppcyme) (2) has been synthesized. H-1, C-13 and P-31 NMR spectroscopy shows that in solution the sterically demanding diphenylphosphine groups occupy equatorial positions on the cyclohexane ring. An X-ray crystal investigation confirms this result for the solid state. Treatment of tdppcyme with Mo(eta(6)-C7H8)(CO)(3) gives Mo(tdppcyme)(CO)(3) (3), with octahedral molybdenum coordination.

  DOI：

  10.1016/0022-328x(94)05316-4

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
• The Mo(CO)₃ Fragment as an Organometallic Protection Group in the Synthesis of Functionalized Tripodal Phosphine Ligands
  作者：Philipp Stössel、Hermann A. Mayer、Cäcilia Maichle-Mössmer、Riad Fawzi、Manfred Steimann

  DOI：10.1021/ic9602512

  日期：1996.1.1

  Treatment of Mo(CO)(6) with cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(methoxycarbonyl)cyclohexane (tdp-pcyme) (L) at elevated temperatures gives Mo(CO)(3)(tdppcyme) (1) in high yield. The ester groups in complex 1 are saponed to carboxylic acid groups by lithium n-propyl mercaptide in DMF and reduced to alcoholic groups by lithium aluminum hydride in THF to yield the carboxylic acid complex 2 and hydroxymethyl complex 4, respectively. Treatment of 1 with ethylenediamine and NaH results in the formation of the carboxamide 3. The methoxymethyl complex 5 is formed from 4 in a phase transfer reaction (THF/aqueous NaOH) with dimethyl sulfate as the methylating agent. Deprotonation of compound 4 with NaH in THF results in the formation of the corresponding trisodium alcoholate which on treatment with chloromethyl methyl ether, 1-methoxy-2-[p-tolylsulfonyl)oxy]ethane, and allyl bromide leads to the corresponding complexes 6-8, respectively. The acid catalyzed addition of the hydroxyl function to 5,6-dihydro-4H-pyran yields the acetal 9. The modified functionalized tripodal phosphines 2a and 5a-9a can be liberated by irradiating solutions of the corresponding molybdenum carbonyl complexes in the presence of pyridine N-oxide or N2O, respectively. No oxidation of the phosphines is observed; MoO3 and CO are obtained. Single-crystal X-ray structure determinations were performed on complexes 3 and 5.