| 752245-70-8

• CAS: 752245-70-8；752250-85-4
• 化学式: C₃₈H₅₇F₆IrO₂P₂
• 分子量: 914.027
• InChiKey: WJADXRGNRFCPTA-ZMKTYRQVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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

• 作为产物：
  描述：

  顺-环辛烯 、 [p-(3,5-CF3)2C6H3C6H2-2,6-(OP(tBu)2)2]IrH2 以 further solvent(s) 为溶剂， 生成 、 、
  参考文献：
  名称：

  Mechanistic Studies of the Transfer Dehydrogenation of Cyclooctane Catalyzed by Iridium Bis(phosphinite) p-XPCP Pincer Complexes

  摘要：

  Reaction of bis(phosphinite) PCP iridium pincer complexes (p-XPCP)IrHCl (5a-f) [X = MeO (5a), Me (5b), H (5c), F (5d), C6F5 (5e), Ar-F(= 3,5-bis(trifluoromethyl)phenyl) (5f)] with NaOtBu in neat cyclooctane (COA) generates 1:1 mixtures of the respective (p-XPCP)IrH2 complexes 4a-f and the cyclooctene (COE) olefin complexes (p-XPCP)lr(COE) (6a-f) at 23 degreesC. At higher temperatures, complexes 4 and 6 are equilibrated because of the degenerate transfer dehydrogenation of COA with free COE (6 + COA = 4 + 2COE), as was shown by temperature-dependent equilibrium constants and spin saturation transfer experiments at 80 degreesC. At this temperature, the COE complexes 6 exchange with free COE on the NMR time scale with the more electron-deficient complexes 6 exchanging COE faster. The exchange is dissociative and zero order in [COE]. Further analysis reveals that the stoichiometric hydrogenation of COE by complex 4f, and thus the separated back reaction 4f + 2COE --> 6f + COA proceeds at temperatures as low as - 100 degreesC with the intermediacy of two isomeric complexes (p-(ArPCP)-P-F)lr(H)(2)(COE) (8f, 8f'). COE deuteration with the perdeuterated complex 4f-d(38) at -100 degreesC results in hydrogen incorporation into the hydridic sites of complexes 8f,8f'-d(38) but not in the hydriclic sites of complex 4f-d(38), thus rendering COE migratory insertion in complexes 8f,8f' reversible and COE coordination by complex 4f rate-determining for the overall COE deuteration.

  DOI：

  10.1021/ja048393f