| 167692-58-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• CAS: 167692-58-2
• 化学式: C₅₁H₅₁O₁₀P₂Rh
• 分子量: 988.813
• InChiKey: UXCPVQACYUJWGL-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：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  、 一氧化碳 以 甲苯 为溶剂， 以93%的产率得到
  参考文献：
  名称：

  Mechanistic Aspects of a Highly Regioselective Catalytic Alkene Hydroformylation using a Rhodium Chelating Bis(phosphite) Complex

  摘要：

  The rhodium-catalyzed hydroformylation of 1-octene using the bis(phosphite) ligand bbmb was studied using in situ, high-pressure H-1 and P-31 NMR and FT-IR spectroscopy. Four species, Rh(bbmb)(acac), Rh(bbmb)(CO)(2)H, and two dimeric complexes, appeared sequentially during different stages of the catalysis when Rh(acac)(CO)(2) was used as the catalyst precursor. These were independently synthesized and their reactivity studied. The major species present during catalysis was determined to be Rh(bbmb)(CO)(2)H (1), which was fully characterized. This hydride complex was shown to be an effective alkene isomerization catalyst. Using magnetization transfer, the rate of exchange between 1 and the terminal and internal vinyl hydrogens of 3,3-dimethylbutene were 0.62 and 0.51 s(-1) respectively. The rapid, reversible nature of the alkene insertion establishes that the regiochemistry of the final aldehyde is not determined at the alkene insertion step or any event prior to it. The dimeric species were shown to convert to 1 via reversible addition of dihydrogen.

  DOI：

  10.1021/om00008a034
• 作为产物：
  描述：

  acetylacetonatodicarbonylrhodium(l) 、 6,6′-[(3,3′-二叔丁基-5,5′-二甲氧基-1,1′-二苯基-2,2′-二基)双(氧)]双(二苯并[d,f][1,3,2]二噁磷杂庚英) 以 甲苯 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  Mechanistic Aspects of a Highly Regioselective Catalytic Alkene Hydroformylation using a Rhodium Chelating Bis(phosphite) Complex

  摘要：

  The rhodium-catalyzed hydroformylation of 1-octene using the bis(phosphite) ligand bbmb was studied using in situ, high-pressure H-1 and P-31 NMR and FT-IR spectroscopy. Four species, Rh(bbmb)(acac), Rh(bbmb)(CO)(2)H, and two dimeric complexes, appeared sequentially during different stages of the catalysis when Rh(acac)(CO)(2) was used as the catalyst precursor. These were independently synthesized and their reactivity studied. The major species present during catalysis was determined to be Rh(bbmb)(CO)(2)H (1), which was fully characterized. This hydride complex was shown to be an effective alkene isomerization catalyst. Using magnetization transfer, the rate of exchange between 1 and the terminal and internal vinyl hydrogens of 3,3-dimethylbutene were 0.62 and 0.51 s(-1) respectively. The rapid, reversible nature of the alkene insertion establishes that the regiochemistry of the final aldehyde is not determined at the alkene insertion step or any event prior to it. The dimeric species were shown to convert to 1 via reversible addition of dihydrogen.

  DOI：

  10.1021/om00008a034

文献信息

• In situ spectroscopic investigations on BiPhePhos modified rhodium complexes in alkene hydroformylation
  作者：Benedict N. Leidecker、Dilver Peña Fuentes、Matthias König、Jiali Liu、Wolfgang Baumann、Mathias Sawall、Klaus Neymeyr、Haijun Jiao、Robert Franke、Armin Börner、Christoph Kubis

  DOI：10.1039/d4cy00481g

  日期：——

  Structural and dynamic properties of BiPhePhos modified rhodium complexes under hydroformylation conditions have been investigated in detail by using high-pressure (HP) in situ transmission IR- and NMR-spectroscopy. An experiment design approach which combines component/reagent perturbations, in situ-FTIR measurements and chemometric peak group analysis (PGA) led to the identification of most relevant

  通过使用高压 (HP) 原位透射红外光谱和核磁共振光谱，详细研究了 BiPhePhos 修饰的铑配合物在加氢甲酰化条件下的结构和动态特性。实验设计方法结合了组分/试剂扰动、原位 FTIR 测量和化学计量峰组分析 (PGA)，从而鉴定出最相关的组分。氢和酰基 18-VE 静息态配合物结构中的配体配位已被阐明。 e,e-[HRh(CO) 2 (P∩P)] 类型的氢化配合物代表催化剂预形成后和 n-区域选择性加氢甲酰化过程中的主要静止状态。在贫氢条件下的严酷反应条件下，二聚体的形成仅发生很小程度。单核和双核氢化单羰基配合物是在较高的配体与金属比率和较低的一氧化碳分压下形成的。双亚磷酸酯改性酰基配合物的两种立体异构形式 e,a-[RC(O)Rh(CO) 2 (P∩P)] 和 e,e-[RC(O)Rh(CO) < b2> (P∩P)] 作为平衡混合物生成。