tricarbonyl[cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(hydroxymethyl)cyclohexane]molybdenum | 182130-52-5

• 英文名称: tricarbonyl[cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(hydroxymethyl)cyclohexane]molybdenum
• 英文别名: tricarbonyl[cis,cis-1,3,5-tris(diphenylphosphanyl)-1,3,5-tris(hydroxymethyl)cyclohexane]molydenum
• CAS: 182130-52-5
• 化学式: C₄₈H₄₅MoO₆P₃
• 分子量: 906.743
• InChiKey: OMAKGXSVOSSHSX-TXSMQXEBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  tricarbonyl[cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(hydroxymethyl)cyclohexane]molybdenum 、 sodium hydride 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Stoesel, Philipp; Mayer, Hermann A.; Auer, Friedrich, European Journal of Inorganic Chemistry, 1998, # 1, p. 37 - 42

  摘要：

  DOI：
• 作为产物：
  描述：

  tricarbonyl[cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(methoxycarbonyl)cyclohexane]molybdenum 、 lithium aluminium tetrahydride 以 四氢呋喃 为溶剂， 以96%的产率得到tricarbonyl[cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(hydroxymethyl)cyclohexane]molybdenum
  参考文献：
  名称：

  The Mo(CO)₃ Fragment as an Organometallic Protection Group in the Synthesis of Functionalized Tripodal Phosphine Ligands

  摘要：

  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.

  DOI：

  10.1021/ic9602512

文献信息

• Stationary phases composed of sol–gel processed organometallic complexes functionalized with polyethylene glycol
  作者：Joachim Büchele、Michael Marzini、Hermann A. Mayer

  DOI：10.1039/b304205g

  日期：——

  A tripodal phosphine molybdenum tricarbonyl complex has been functionalized with polyethylene glycol spacers of average chain lengths ranging from 0 to 90. Hydrolysable end groups were attached to the spacers via a platinum catalysed hydrosilylation, a Williamson ether synthesis Cl(CH2)3Si(OEt)3 and an addition reaction of OCN(CH2)3Si(OEt)3. The resulting complexes were sol–gel processed by two different

  三脚架膦膦三羰基钼配合物已用平均链长为0至90的聚乙二醇间隔基进行了功能化。可水解的端基通过铂催化的方式连接到间隔基上氢化硅烷化，Williamson醚合成Cl（CH 2）3 Si（OEt）3和OCN（CH 2）3 Si（OEt）3的加成反应。通过两种不同的方法，以不同量的Si（OMe）4和Si（OEt）4作为共缩合剂，对所得复合物进行溶胶-凝胶处理。这样产生的有机金属/无机杂化材料具有取决于间隔物长度和共缩合剂的量的特征。详细的多核核磁共振 光谱研究确定了金属配合物的结构。 聚合物并揭示出材料的交联度和缩合度。此外，弛豫研究使人们深入了解了杂化物中金属络合物的动力学。聚合物。相间化学反应是使用选定的材料进行的。三羰基钼碎片通过光化学/氧化相结合的方法除去，留下三脚架膦 在里面 聚合物。这些聚合了膦类 用作新的铑和铱配合物的起始材料，它们是固定相中的反应中心。