[(2,6-C6H3(CH2P(CF3)2)2)Ir(η4-norbornene)] | 1268160-22-0

• 英文名称: [(2,6-C6H3(CH2P(CF3)2)2)Ir(η4-norbornene)]
• 英文别名: [(1,3-C6H3(CH2P(CF3)2)2)Ir(norbornadiene)]
• CAS: 1268160-22-0
• 化学式: C₁₉H₁₅F₁₂IrP₂
• 分子量: 725.476
• InChiKey: GKUFUGWBXBJCLH-IDMSHCHPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  1,5-环辛二烯 、 [(2,6-C6H3(CH2P(CF3)2)2)Ir(η4-norbornene)] 以 further solvent(s) 为溶剂， 生成 [(2,6-C6H3(CH2P(CF3)2)2)Ir(η4-cyclooctadiene)]
  参考文献：
  名称：

  Investigation of Iridium^CF₃PCP Pincer Catalytic Dehydrogenation and Decarbonylation Chemistry

  摘要：

  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.

  DOI：

  10.1021/om2011886
• 作为产物：
  描述：

  [(1,3-C6H3(CH2P(CF3)2)2)Ir(H)Cl(η2-C2H4)] 、 2,5-降冰片二烯 在 Et₃N 作用下， 以 苯 为溶剂， 以81%的产率得到[(2,6-C6H3(CH2P(CF3)2)2)Ir(η4-norbornene)]
  参考文献：
  名称：

  受体PCP钳制铱（I）化学：稳定非子午线PCP配位几何

  摘要：

  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

  DOI：

  10.1021/om100864g