[Ir(C6H4CH2NEt2-2-C,N)(cycloocta-1,5-diene)] | 185384-98-9

• 英文名称: [Ir(C6H4CH2NEt2-2-C,N)(cycloocta-1,5-diene)]
• CAS: 185384-98-9
• 化学式: C₁₉H₂₈IrN
• 分子量: 462.658
• InChiKey: INWITVPOAQXQIS-GHDUESPLSA-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：
  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：

  [Ir(C6H4CH2NEt2-2-C,N)(cycloocta-1,5-diene)] 、 碘甲烷 以 甲苯 为溶剂， 以95%的产率得到[Ir(C6H4CH2NEt(CHMe)-2-C,N,C')I(cycloocta-1,5-diene)]
  参考文献：
  名称：

  Intramolecular CH activation and oxidative addition reactions of iridium complexes containing arylamines with bulky substituents on n itrogen; X-ray structures of [IrI(C6H4CH2NEt2-2-C,C)] and [IrIII(C6H4CH2Net(CHMe)-2-C,N,C′)I(cod)] (cod = cycloocta-1,-5-diene)

  摘要：

  Square-planar iridium(I) complexes [Ir(C(6)H(4)CH(2)NRR') (cod)] (R = R' = Et; R = Me, R' = t-Bu; cod = cycloocta-1,5-diene) containing C,N-chelating arylamine ligands have been synthesized and characterized by NMR spectroscopy. An X-ray diffraction study of [Ir(C(6)H(4)CH(2)NEt(2)-2-C,N) (cod)] shows a weak agostic interaction between the d(8) metal center and a methyl H atom of one ethyl group. An oxidative addition reaction of this complex with MeI affords an Ir(III) complex [Ir(C(6)H(4)CH(2)NEt(CHMe)-2-C,N,C')I(cod)] which results from an intramolecular methylene C-H activation process. This latter complex has been characterized with 2D NMR techniques and an X-ray diffraction study. The reactivity of the new iridium(I) complexes as well as [Ir(C(6)H(4)CH(2)NMe(2)-2-C,N) (cod)], [Ir(1-C(10)H(6)NMe(2)-8-C,N) (cod)] and [Ir(C6H4CH2N(Me)CH(2)CH(2)NMe(2)-2-C,N) (cod)] towards H-2 is reported; the different products obtained are discussed with reference to reaction pathways influenced by the steric bulk on the nitrogen donor atom. Crystals of [Ir(C(6)H(4)CH(2)NEt(2)-2-C,N)(cod)] are triclinic, space group P (1) over bar with unit-cell dimensions a = 9.154(1), b = 9.992(1), c = 10.846(1) Angstrom, (alpha = 93.46(1), beta = 113.03(1), gamma = 109.84(1)degrees, Z = 2, final R = 0.0234, wR = 0.0295 for 3465 reflections with I>2.5 sigma(I) and 197 parameters. Crystals of [Ir(C(6)H(4)CH(2)NEt(CHMe>-2-C,N,C')I(cod)] are triclinic, space group P (1) over bar with dimensions a = 7.591(1), b = 11.406(1), c = 13.511(1) Angstrom, alpha = 65.63(1), beta = 88.34(1), gamma = 83.29(1)degrees, Z = 2, final R = 0.0319, wR = 0.0402 for 4236 reflections with I>2.5 sigma(I) and 228 parameters.

  DOI：

  10.1016/s0020-1693(96)05298-x
• 作为产物：
  描述：

  o-diethylanilinelithium 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 以 苯 为溶剂， 以93%的产率得到[Ir(C6H4CH2NEt2-2-C,N)(cycloocta-1,5-diene)]
  参考文献：
  名称：

  Intramolecular CH activation and oxidative addition reactions of iridium complexes containing arylamines with bulky substituents on n itrogen; X-ray structures of [IrI(C6H4CH2NEt2-2-C,C)] and [IrIII(C6H4CH2Net(CHMe)-2-C,N,C′)I(cod)] (cod = cycloocta-1,-5-diene)

  摘要：

  Square-planar iridium(I) complexes [Ir(C(6)H(4)CH(2)NRR') (cod)] (R = R' = Et; R = Me, R' = t-Bu; cod = cycloocta-1,5-diene) containing C,N-chelating arylamine ligands have been synthesized and characterized by NMR spectroscopy. An X-ray diffraction study of [Ir(C(6)H(4)CH(2)NEt(2)-2-C,N) (cod)] shows a weak agostic interaction between the d(8) metal center and a methyl H atom of one ethyl group. An oxidative addition reaction of this complex with MeI affords an Ir(III) complex [Ir(C(6)H(4)CH(2)NEt(CHMe)-2-C,N,C')I(cod)] which results from an intramolecular methylene C-H activation process. This latter complex has been characterized with 2D NMR techniques and an X-ray diffraction study. The reactivity of the new iridium(I) complexes as well as [Ir(C(6)H(4)CH(2)NMe(2)-2-C,N) (cod)], [Ir(1-C(10)H(6)NMe(2)-8-C,N) (cod)] and [Ir(C6H4CH2N(Me)CH(2)CH(2)NMe(2)-2-C,N) (cod)] towards H-2 is reported; the different products obtained are discussed with reference to reaction pathways influenced by the steric bulk on the nitrogen donor atom. Crystals of [Ir(C(6)H(4)CH(2)NEt(2)-2-C,N)(cod)] are triclinic, space group P (1) over bar with unit-cell dimensions a = 9.154(1), b = 9.992(1), c = 10.846(1) Angstrom, (alpha = 93.46(1), beta = 113.03(1), gamma = 109.84(1)degrees, Z = 2, final R = 0.0234, wR = 0.0295 for 3465 reflections with I>2.5 sigma(I) and 197 parameters. Crystals of [Ir(C(6)H(4)CH(2)NEt(CHMe>-2-C,N,C')I(cod)] are triclinic, space group P (1) over bar with dimensions a = 7.591(1), b = 11.406(1), c = 13.511(1) Angstrom, alpha = 65.63(1), beta = 88.34(1), gamma = 83.29(1)degrees, Z = 2, final R = 0.0319, wR = 0.0402 for 4236 reflections with I>2.5 sigma(I) and 228 parameters.

  DOI：

  10.1016/s0020-1693(96)05298-x