(2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene)Rh(CO)2H | 251967-84-7

• 英文名称: (2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene)Rh(CO)2H
• 英文别名: [RhH(CO)2(4,5-bis(diphenylphosphino)-2,7-di-tert-butyl-9,9-dimethylxanthene)]
• CAS: 251967-84-7
• 化学式: C₄₉H₄₉O₃P₂Rh
• 分子量: 850.779
• InChiKey: RLZQEJUJBIVRQY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  acetylacetonatodicarbonylrhodium(l) 、 1,1'-[2,7-bis(1,1-dimethylethyl)-9,9-dimethyl-9H-xanthene-4,5-diyl]bis[1,1-diphenylphosphine] 以 氘代苯 为溶剂， 生成 (2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene)Rh(CO)2H 、 氢气
  参考文献：
  名称：

  New Phosphacyclic Diphosphines for Rhodium-Catalyzed Hydroformylation

  摘要：

  The use of phosphacyclic diphosphines based on the xanthene backbone as ligands in rhodium-catalyzed hydroformylation was studied. New phosphacyclic xantphos ligands with wide natural bite angles were synthesized, and a short, efficient route toward the synthesis of 10-chlorophenoxaphosphine and 10-chlorophenothiaphosphine was developed. The effect of the phosphacyclic moieties on the coordination chemistry in the (diphosphine)Rh(CO)(2)H complexes was investigated using NMR and IR spectroscopy. Both NMR and IR spectroscopy showed that the phosphacyclic xantphos ligands exhibit an enhanced preference for diequatorial(ee) chelation compared to the diphenylphosphino-substituted parent compound. In the hydroformylation of 1-octene the introduction of the phosphacyclic moieties leads to higher reaction rates. More importantly, the dibenzophospholyl- and phenoxaphosphino-substituted xantphos ligands exhibit an unprecedented high activity and selectivity in the hydroformylation of trans 2- and 4-octene to linear nonanal. The high activities of the phosphacyclic xantphos ligands are explained by the lower phosphine basicity and the wider natural bite angles of the phosphacyclic ligands. The extraordinary high activity of the phenoxaphosphino - substituted xantphos ligand can be attributed to the 4- to 6 -fold higher rate of CO dissociation compared to the other xantphos ligands. CO dissociation rates from the (diphosphine)Rh(Co)(2)H complexes were determined using (CO)-C-13 labeling in rapid-scan IR experiments.

  DOI：

  10.1021/om990523j

文献信息

• Phenoxaphosphine-Based Diphosphine Ligands. Synthesis and Application in the Hydroformylation Reaction
  作者：Erik Zuidema、P. Elsbeth Goudriaan、Bert H. G. Swennenhuis、Paul C. J. Kamer、Piet W. N. M. van Leeuwen、Martin Lutz、Anthony L. Spek

  DOI：10.1021/om901041r

  日期：2010.3.8

  to an increase in catalytic activity and a decrease in regioselectivity toward the linear aldehyde product. Xanthene-based ligands 1a−1c yielded highly active and regioselective hydroformylation catalysts; ligands containing p-tolyl ether and ferrocene backbones 2a−2c and 3a−3c provided less active and less regioselective catalysts. Catalysts containing benzene-derived ligands 4a and 4b showed a remarkable

  基于2,7-二叔丁基-9,9-二甲基x吨（1），对甲苯基醚（2），二茂铁（3）和苯（4）主链的一系列新的二膦配体的合成，据报道，它含有一个或两个2，8-二甲基苯氧杂膦部分。所述配体用于铑催化的1-辛烯的加氢甲酰化。对于所有四个配体主链，苯氧磷膦部分的引入导致催化活性的增加和对线性醛产物的区域选择性的降低。基于an吨的配体1a - 1c产生了高活性和区域选择性的加氢甲酰化催化剂。含p-的配体甲苯基醚和二茂铁骨架2a - 2c和3a - 3c提供了较低的活性和较低的区域选择性催化剂。含有苯衍生的配体4a和4b的催化剂表现出显着的偏爱于形成支链醛产物。配体的协调行为1 - 4使用高压NMR和IR光谱加氢甲酰化条件下进行了研究，揭示在配体的二苯基膦的不同空间和电子属性和2,8- dimethylphenoxaphosphine部分1 - 4。事实证明，与无环二苯基膦部分相比，磷环部分对金属配合物中