cis-1,3-bis(di-tert-butylphosphinito)cyclohexane | 1002099-25-3

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: cis-1,3-bis(di-tert-butylphosphinito)cyclohexane
• 英文别名: ditert-butyl-[(1R,3S)-3-ditert-butylphosphanyloxycyclohexyl]oxyphosphane
• CAS: 1002099-25-3
• 化学式: C₂₂H₄₆O₂P₂
• 分子量: 404.554
• InChiKey: REUNCSHBGNCHSZ-HDICACEKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  dichloro( 1,5-cyclooctadiene)platinum(ll) 、 cis-1,3-bis(di-tert-butylphosphinito)cyclohexane 以 四氢呋喃 为溶剂， 以86%的产率得到trans-[PtCl2(cis-1,3-bis(di-tert-butylphosphinito)cyclohexane)]2
  参考文献：
  名称：

  Synthesis and characterisation of PCsp3P phosphine and phosphinite platinum(ii) complexes. Cyclometallation and simple coordination

  摘要：

  报道了先前已知的PCP配体顺-1,3-双(二异丙基膦基)环​​己烷和顺-1,3-双[(二叔丁基膦基)甲基]环己烷的新的和改进的制备路线。它们与 1 当量的二氯(1,5-环辛二烯)铂(II) [(COD)PtCl2] 反应，得到顺式配位络合物 cis-[PtCl2{cis-1,3-双(二异丙基次膦基)}环己烷]和Csp3-H活化的复合物反式-[PtCl{cis-1,3-双(二叔丁基膦)}环己烷]。合成了新的 PCP 配体 cis-1,3-bis(二叔丁基亚膦基)环己烷，并与 [(COD)PtCl2] 反应，得到双核反式-[PtCl2{cis-1,3-bis(di-)叔丁基亚膦基)环己烷}]2，高度不溶。所有金属配合物均采用 X 射线晶体学进行表征。 DFT 计算表明，次亚膦酸酯配体无法环金属化是由于动力学势垒，可能涉及 C-H 活化过程所需的轴-赤道构象变化。

  DOI：

  10.1039/b712660c
• 作为产物：
  描述：

  二叔丁基氯化膦 、 cis-1,3-cyclohexanediol 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 31.0h， 以89%的产率得到cis-1,3-bis(di-tert-butylphosphinito)cyclohexane
  参考文献：
  名称：

  Synthesis and characterisation of PCsp3P phosphine and phosphinite platinum(ii) complexes. Cyclometallation and simple coordination

  摘要：

  报道了先前已知的PCP配体顺-1,3-双(二异丙基膦基)环​​己烷和顺-1,3-双[(二叔丁基膦基)甲基]环己烷的新的和改进的制备路线。它们与 1 当量的二氯(1,5-环辛二烯)铂(II) [(COD)PtCl2] 反应，得到顺式配位络合物 cis-[PtCl2{cis-1,3-双(二异丙基次膦基)}环己烷]和Csp3-H活化的复合物反式-[PtCl{cis-1,3-双(二叔丁基膦)}环己烷]。合成了新的 PCP 配体 cis-1,3-bis(二叔丁基亚膦基)环己烷，并与 [(COD)PtCl2] 反应，得到双核反式-[PtCl2{cis-1,3-bis(di-)叔丁基亚膦基)环己烷}]2，高度不溶。所有金属配合物均采用 X 射线晶体学进行表征。 DFT 计算表明，次亚膦酸酯配体无法环金属化是由于动力学势垒，可能涉及 C-H 活化过程所需的轴-赤道构象变化。

  DOI：

  10.1039/b712660c

文献信息

• Synthesis and characterisation of PCsp3P phosphine and phosphinite iridium complexes. Cyclometallation and dehydrogenation of a cyclohexyl ring
  作者：Athimoolam Arunachalampillai、Daniel Olsson、Ola F. Wendt

  DOI：10.1039/b910798c

  日期：——

  pincer phosphine ligand undergoes cyclometalation with an iridium cyclooctadiene precursor to give a highly thermally stable iridium(III) complex where a C(sp3)-H bond has been oxidatively added. This iridium(III) hydride complex is reduced with potassium to give a terminal iridium(I) dinitrogen complex with no tendency to dimerization. The corresponding cyclohexyl phosphinite ligand undergoes reversible

  基于环己基的钳制膦配体与铱环辛二烯前体进行环金属化反应，得到高度热稳定的铱（III）络合物，其中已氧化氧化了C（sp3）-H键。该氢化铱（III）配合物用钾还原，得到末端铱（I）二氮配合物，没有二聚化的趋势。相应的环己基次膦酸酯配体经过可逆脱氢反应，得到芳族环金属化氢化铱（III）氢化物配合物，以及3个当量的二氢。
• Cyclohexane-Based Phosphinite Iridium Pincer Complexes: Synthesis, Characterization, Carbene Formation, and Catalytic Activity in Dehydrogenation Reactions
  作者：Alexey V. Polukeev、Ola F. Wendt

  DOI：10.1021/acs.organomet.6b00846

  日期：2017.2.13

  Metalation of two cyclohexane-based phosphinite pincer ligands, cis-POCyPO (4) and trans-POCyPO (5) (POCyPO = 1,3-bis-[(di-tert-butylphosphinito]-cydoliexane}(-)), is reported. In line with previously published results (Dalton Trans. 2009, 8626, DOI: 10.1039/b910798c), ligand. 4 undergoes aromatization to give benzene-based complex (POCOP)IrHC1 (3) at high temperatures in the presence of [It(COD)C1](2). However, here we present the isolation of carbene complex (POCy0P)= IrC1 (6) which is an intermediate in the aromatization process; upon reaction with H-2, 6 can be readily transformed to the corresponding hydridochloride 8. Metalation of trans-POCyOP ligand 5 gives hydridochloride 13 which only upon further heating can be converted to the corresponding carbene 14. A mechanistic study of hydrogenation of carbene 6 is reported, as well as interesting ambient temperature CO-induced C H activation in beta-position of 6, a process that under other circumstances takes place around 200 degrees C. The cis complex (POCyOP)IrHCI (8), upon activation with base, revealed moderate activity in transfer dehydrogenation of cydooetane (144 turnover numbers (TON)), while the performance of trans analog 13 was much better (up to 1684 TON). Carbene complex 6 and in situ generated 14 demonstrated promising activity in acceptorless dehydrogenation of alcohols, presumably operating via a novel metal ligand cooperation type mechanism. Some of the alcohol dehydrogenations generated large amounts of polystyrene.
• Synthesis and characterisation of PCsp3P phosphine and phosphinite platinum(ii) complexes. Cyclometallation and simple coordination
  作者：Daniel Olsson、Athimoolam Arunachalampillai、Ola F. Wendt

  DOI：10.1039/b712660c

  日期：——

  New and improved preparative routes to the previously known PCP ligands cis-1,3-bis(di-isopropylphosphinito)cyclohexane and cis-1,3-bis[(di-tert-butylphosphino)methyl]cyclohexane are reported. They react with 1 equivalent of dichloro(1,5-cyclooctadiene)platinum(II) [(COD)PtCl2] to give the cis coordinated complex cis-[PtCl2cis-1,3-bis(di-isopropylphosphinito)}cyclohexane] and the Csp3-H activated complex trans-[PtClcis-1,3-bis(di-tert-butylphosphino)}cyclohexane]. The new PCP ligand cis-1,3-bis(di-tert-butylphosphinito)cyclohexane was synthesised and reacts with [(COD)PtCl2] giving the di-nuclear trans-[PtCl2cis-1,3-bis(di-tert-butylphosphinito)cyclohexane}]2, which is highly insoluble. All metal complexes were characterised with X-ray crystallography. DFT calculations indicate that the inability of the phosphinite ligands to cyclometallate is due to a kinetic barrier, possibly involving an axial–equatorial conformational change necessary for the C–H activation process.

  报道了先前已知的PCP配体顺-1,3-双(二异丙基膦基)环​​己烷和顺-1,3-双[(二叔丁基膦基)甲基]环己烷的新的和改进的制备路线。它们与 1 当量的二氯(1,5-环辛二烯)铂(II) [(COD)PtCl2] 反应，得到顺式配位络合物 cis-[PtCl2cis-1,3-双(二异丙基次膦基)}环己烷]和Csp3-H活化的复合物反式-[PtClcis-1,3-双(二叔丁基膦)}环己烷]。合成了新的 PCP 配体 cis-1,3-bis(二叔丁基亚膦基)环己烷，并与 [(COD)PtCl2] 反应，得到双核反式-[PtCl2cis-1,3-bis(di-)叔丁基亚膦基)环己烷}]2，高度不溶。所有金属配合物均采用 X 射线晶体学进行表征。 DFT 计算表明，次亚膦酸酯配体无法环金属化是由于动力学势垒，可能涉及 C-H 活化过程所需的轴-赤道构象变化。