(η⁴-1,5-cyclooctadiene)(iodo)(methyl)(thioacetylacetonato)iridium(III) | 169135-98-2

• 英文名称: (η⁴-1,5-cyclooctadiene)(iodo)(methyl)(thioacetylacetonato)iridium(III)
• 英文别名: [Ir(cod)(sacac)(CH3)I]；[Ir(cod)(thioacetylacetonato)(CH3)I]
• CAS: 169135-98-2
• 化学式: C₁₄H₂₂IIrOS
• 分子量: 557.519
• InChiKey: YWXILFJEUQCMIS-SUESZSCISA-M

反应信息

• 作为产物：
  描述：

  (η(4)-1,5-cyclooctadiene)(thioacetylacetonato)iridium 、 碘甲烷 以 丙酮 为溶剂， 生成 (η⁴-1,5-cyclooctadiene)(iodo)(methyl)(thioacetylacetonato)iridium(III)
  参考文献：
  名称：

  (η4-1,5-Cyclooctadiene)(iodo)(methyl)(thioacetylacetonato)iridium(III)

  摘要：

  The structure determination of the title complex, [Ir(C5H7OS)(CH3)(I)(C8H12)], revealed that the oxidative addition of iodomethane to (eta(4) -1,5-cyclooctadiene)(thioacetylacetonato)iridium(I) results in the formation of the trans isomer. The deviation of the I-Ir-CH3 angle [156.1(3)degrees] from linearity is attributed to steric repulsion between the CH3 group or I atom and the olefinic H atoms.

  DOI：

  10.1107/s010827019500254x

文献信息

• Characterisation and mechanistic study of the oxidative addition reactions of [Ir(cod)(sacac)]
  作者：Walter Purcell、Jeanet Conradie、Sumit Kumar、Johan A. Venter

  DOI：10.1016/j.jorganchem.2015.10.012

  日期：2016.1

  [Ir(cod)(sacac)] (sacac = thioacetyl acetonato) complexes were successfully synthesized and characterised using H-1 and C-13 NMR, IR and micro elemental analyses. The formation of isosbestic points in different solvents clearly indicate the formation of only one product, while the kinetic results for all of the complexes (except for chlorobenzene) showed simple second order kinetics with a zero intercept (within experimental error). The rate of oxidative addition showed little or no change with a solvent variation even with a large difference in polarity for the selected solvents, varying between 1.78 x 10(-3) and 5.2(3) M-1 s(-1) for chlorobenzene and acetonitrile respectively. Activation volumes were determined in four of the solvents, which varied between +10.2(9) for chloroform to -18(1) cm(3) mol(-1) for acetonitrile. This solvent variation obeyed the Kirkwood equation with an intrinsic volume of activation of -21(3) cm(3). A DFT analysis of the oxidative addition reaction shows that the trans addition is energetically favoured and that the trans [Ir(cod) (sacac) (CH3) (I)]-alkyl product is more stable than the four possible cis [Ir(cod) (sacac) (CH3) (I)]-alkyl products. (C) 2015 Elsevier B.V. All rights reserved.