(PNP(iPr))Re(H)(C-CH2CMe3) | 714264-21-8

• 英文名称: (PNP(iPr))Re(H)(C-CH2CMe3)
• CAS: 714264-21-8
• 化学式: C₂₄H₅₆NP₂ReSi₂
• 分子量: 663.041
• InChiKey: NNGPNZIGRQQMJT-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

• 作为产物：
  描述：

  3,3-二甲基-1-丁烯 、 (PNP(iPr))ReH4 以 not given 为溶剂， 生成 (PNP(iPr))Re(H)(C-CH2CMe3) 、
  参考文献：
  名称：

  Transformation of Acyclic Alkenes to Hydrido Carbynes by (PNP^R)Re Complexes

  摘要：

  Synthesis of (PNPR)ReOCl2 (PNPR = (R2PCH2SiMe2)(2)N, R = Pr-i, Cy, and Bu-t) from (Me2S)(2)-ReOCl3 and (PNPR)MgCl is described. Magnesium and H-2 convert (PNPR)ReOCl2 first to (PNPR)ReO(H)(2) and then to (PNPR)Re(H)(4), the last being an operationally unsaturated species which can bind PMe3 or p-toluidine. Acyclic alkenes react with (PNPR)Re(H)(4) at 22 degreesC to give first (PNPR)Re(H)(2)(olefin) and then (PNPR)ReH(carbyne), in equilibrium with its eta(2)-olefin adduct. Re can also migrate to the terminal carbon of internal olefins to form a carbyne complex. Allylic C-SiMe3 or C-NH2 bonds are not broken, but OEt, OPh, and F vinyl substituents (X) are ultimately cleaved from carbon to give the Reequivalent toC-CH3 complex and liberate HX. DFT calculations, together with detection of intermediates for certain olefins, help to define a mechanism for these conversions.

  DOI：

  10.1021/ja031617u

文献信息

• Operationally Unsaturated Pincer/Rhenium Complexes Form Metal Carbenes from Cycloalkenes and Metal Carbynes from Alkanes
  作者：Oleg V. Ozerov、Lori A. Watson、Maren Pink、Kenneth G. Caulton

  DOI：10.1021/ja062327r

  日期：2007.5.1

  equilibrium with its carbene isomer; at 90 degrees C, hydrocarbon ligand Calpha-Cbeta bond cleavage occurs to give, for the first time, a carbyne complex from an internal olefin. Two compounds synthesized here have the formal composition "(PNPR)Re + olefin", and each of these is capable of dehydrogenating the methyl group of a variety of alkanes at 110 degrees C to form (PNP)ReH triple bond (CR).

  操作不饱和（即 16/18 电子）(PNPR)Re(H)4，其中 PNPR 是 N(SiMe2CH2PR2)2，在 22 摄氏度时与环烯烃反应。首先观察到的产物通常是 (PNPR)Re(H)2(亚环烷基)，氢化烯烃是从四氢化物中夺氢的产物。R = tBu 的四氢化物络合物通常无法反应（体积太大），R = 环己基有（可控的）从一个环中提取 3H 的趋势，形成 eta3-环己烯基化合物，而 R = iPr 通常得到最丰富的双分子反应性。所研究的环状单烯烃显示出不同的反应性，C6 先生成卡宾，然后配位环己二烯，C5 生成卡宾，然后是二烯，然后是 eta5-C5H5，C8 生成卡宾，然后是 eta2-环辛炔，C12 生成 eta3-烯丙基。降冰片烯与卡宾异构体在热平衡状态下生成 pi 络合物；在 90 摄氏度时，烃配体 Cα-Cβ 键发生断裂，第一次从内烯烃生成碳炔配合物。这里合成的两种化合物的正式组成为“(PNPR)Re