[(1,3-C6H3(CH2P(CF3)2)2)Ir(H)Cl(η2-C2H4)] | 1266146-97-7

• 英文名称: [(1,3-C6H3(CH2P(CF3)2)2)Ir(H)Cl(η2-C2H4)]
• 英文别名: [(1,3-C6H3(CH2P(CF3)2)2)Ir(C2H4)(H)Cl]；[(2,6-C6H3(CH2P(CF3)2)2)Ir(C2H4)(H)Cl]
• CAS: 1266146-97-7
• 化学式: C₁₄H₁₂ClF₁₂IrP₂
• 分子量: 697.851
• InChiKey: XFWOCUUWUFUXHS-UHFFFAOYSA-M

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：

  乙腈 、 [(1,3-C6H3(CH2P(CF3)2)2)Ir(H)Cl(η2-C2H4)] 以 乙腈 为溶剂， 生成 [(1,3-C6H3(CH2P(CF3)2)2)Ir(H)Cl(CH3CN)]
  参考文献：
  名称：

  受体PCP钳形铱化学：（CF 3 PCP）Ir III配位性质

  摘要：

  报道了掺有贫电子钳式配体（1,3-C 6 H 3（CH 2 P（CF 3）2）2）（CF 3 PCP）的Ir（I）和Ir（III）配合物的合成。在温和条件下，反应CF 3 PCPH与[（COD）的Ir（μ-Cl）的] 2在苯，得到聚合物[（COD）的IrCl（μ- CF 3 PCPH）] Ñ，其在结构上表征。[（coe）2 Ir（μ-Cl）] 2或[（cod）Ir（μ-Cl）] 2用CF 3的热分解120°C的甲苯中的PCPH导致金属化，生成的不是预期的16电子（CF 3 PCP）Ir（H）Cl产物，而是配位饱和的CF 3 PCPH桥联二聚体{（CF 3 PCP）Ir（H） CL} 2（μ- CF 3 PCPH）。容易置换桥接的CF 3 PCPH配体，以提供单体产物（CF 3 PCP）Ir（L）（H）Cl（L = CO，MeCN）; （CF 3 PCP）Ir（L）（H）Cl（L = CO，MeCN，PhCN，C

  DOI：

  10.1021/om1008633
• 作为产物：
  描述：

  乙烯 、 ^CF3PCPH 、 chlorobis(cyclooctene)-iridium(I) dimer 以 甲苯 为溶剂， 以69%的产率得到[(1,3-C6H3(CH2P(CF3)2)2)Ir(H)Cl(η2-C2H4)]
  参考文献：
  名称：

  受体PCP钳形铱化学：（CF 3 PCP）Ir III配位性质

  摘要：

  报道了掺有贫电子钳式配体（1,3-C 6 H 3（CH 2 P（CF 3）2）2）（CF 3 PCP）的Ir（I）和Ir（III）配合物的合成。在温和条件下，反应CF 3 PCPH与[（COD）的Ir（μ-Cl）的] 2在苯，得到聚合物[（COD）的IrCl（μ- CF 3 PCPH）] Ñ，其在结构上表征。[（coe）2 Ir（μ-Cl）] 2或[（cod）Ir（μ-Cl）] 2用CF 3的热分解120°C的甲苯中的PCPH导致金属化，生成的不是预期的16电子（CF 3 PCP）Ir（H）Cl产物，而是配位饱和的CF 3 PCPH桥联二聚体{（CF 3 PCP）Ir（H） CL} 2（μ- CF 3 PCPH）。容易置换桥接的CF 3 PCPH配体，以提供单体产物（CF 3 PCP）Ir（L）（H）Cl（L = CO，MeCN）; （CF 3 PCP）Ir（L）（H）Cl（L = CO，MeCN，PhCN，C

  DOI：

  10.1021/om1008633

文献信息

• Acceptor PCP Pincer Iridium(I) Chemistry: Stabilization of Nonmeridional PCP Coordination Geometries
  作者：Jeramie J. Adams、Navamoney Arulsamy、Dean M. Roddick

  DOI：10.1021/om100864g

  日期：2011.2.28

  of a series of four-coordinate complexes (CF3PCP)Ir(L) (L = CO, DBU, nbe, coe, MeP(C2F5)2 (dfmp)) and five-coordinate complexes (CF3PCP)Ir(L)(L′) (L = L′ = CO, dfmp, nbd, cod, (C2F5)2PCH2CH2P(C2F5)2 (dfepe); L = PhCN, L′ = C2H4) from dehydrohalogenation of (CF3PCP)Ir(C2H4)(H)Cl with Et3N in the presence of trapping ligands is reported. (CF3PCP)Ir(L) and (CF3PCP)Ir(L)2 for L = CO, dfmp have been structurally

  制备一系列四坐标配合物（CF 3 PCP）Ir（L）（L = CO，DBU，nbe，coe，MeP（C 2 F 5）2（dfmp））和五坐标配合物（CF 3 PCP）Ir（L）（L'）（L = L'= CO，dfmp，nbd，cod，（C 2 F 5）2 PCH 2 CH 2 P（C 2 F 5）2（dfepe）; L = PhCN （CF 3 PCP）Ir（C 2 H 4）（H）Cl与Et 3的脱卤化氢，L'= C 2 H 4）据报道，N存在于俘获配体中。（CF 3 PCP）Ir（L）和（CF 3 PCP）Ir（L）2（对于L = CO，dfmp）已进行结构表征，并建立了（CF 3 PCP）Ir（L）的扭曲三角双锥体配位几何2具有弯曲的PCP单元和不等的轴向和赤道L坐标位置。（CF 3 PCP）Ir（L）（L'）系统（L = L'= CO，C 2 H 4 ; L = PhCN，L'= C
• Investigation of Iridium^CF₃PCP Pincer Catalytic Dehydrogenation and Decarbonylation Chemistry
  作者：Jeramie J. Adams、Navamoney Arulsamy、Dean M. Roddick

  DOI：10.1021/om2011886

  日期：2012.2.27

  The iridium fluorinated pincer complex ((PCP)-P-CF3)Ir-(cod) ((PCP)-P-CF3 = 2,6-C6H3(CH2P(CF3)(2))(2)) catalyzes hydrogen transfer from cyclooctane (coa) to tert-butylethylene (tbe) in 1/1 coa/tbe at 200 degrees C to give cyclooctene (coe) and neohexane (tba) at an initial rate of 40 TO h(-1). In 5/1 coa/tbe, higher initial activity (155 TO h(-1)) and higher turnovers (2580 TON's after 1450 min) are found. Samples of 95% the contain significant amounts of isoprene (2-methyl-1,3-butadiene), which reacts with ((PCP)-P-CF3)Ir(cod) to initially form ((PCP)-P-CF3)Ir(isoprene). Alkene inhibition studies show that ((PCP)-P-CF3)Ir is only modestly inhibited (67% reduced initial activity) in the presence of 800 equiv of added coe. Unlike donor pincer systems, no decrease in activity is noted under 1 atm of N-2 or in the presence of excess water. Hydrogenation of ((PCP)-P-CF3)Ir(L) (L = cod, isoprene) did not produce ((PCP)-P-CF3)Ir(H)(x) but instead afforded the first example of the unusual aryl-bridged bimetallic complex [(mu-1 kappa(2)(P,C),2 kappa(2)(P',C)-(PCP)-P-CF3)Ir(H)(2)](2)(mu-(PCPH)-P-CF3)(mu-H), which has been isolated and crystallographically characterized. Ir(I) pincer complexes ((PCP)-P-CF3)Ir(L) (L = MeP(C2F5)(2), CO, dfepe (dfepe = (C2F5)(2)PCH2CH2P(C2F5)(2))) also serve as moderately active aldehyde decarbonylation catalyst precursors for 2-naphthaldehyde with similar activities in diglyme (1.7 TO h(-1), 152 degrees C) and in 1,4-dioxane (0.052 TO h(-1), 94 degrees C). The catalyst resting states are the corresponding five-coordinate carbonyl complexes ((PCP)-P-CF3)Ir(MeP(C2F5)(2))(CO), ((PCP)-P-CF3)Ir(CO)(2), and [((PCP)-P-CF3)Ir-(CO)](2)(mu-dfepe) (CO)](2)(mu-dfepe). DFT studies indicate that the preferred catalyst resting state for alkane dehydrogenation, ((PCP)-P-CF3)Ir-(cod), can be ascribed to the lower steric requirements of the CF3-substituted pincer ligand.