| 136736-40-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 136736-40-8
• 化学式: C₃₉H₄₉IrNP₃Si₂
• 分子量: 873.137
• InChiKey: AJVKTSAOSOLTPX-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  以 甲苯 为溶剂， 以80%的产率得到
  参考文献：
  名称：

  Thermal and photochemical transformations of organoiridium phosphide complexes. Mechanistic studies on carbon-phosphorus bond formation to generate cyclometalated hydride complexes by .alpha.-hydride abstraction

  摘要：

  The thermal and photolytic transformations of a series of methyliridium(III) phosphide complexes are described. Complexes of the formula Ir(CH3)PR2[N(SiMe2CH2PPh2)2] (R = Ph, Me) rearrange thermally to generate the corresponding cyclometalated derivatives fac-Ir(eta-2-CH2PR2)H[N(SiMe2CH2PPh2)2]; continued thermolysis results in the formation of the iridium(I) phosphine complexes Ir(PMeR2)[N(SiMe2CH2PPh2)2]. Under photolytic conditions the phosphide derivatives rearrange directly to the phosphine complexes with no observable intermediates. The phenylphosphide complex Ir(CH3)PHPh[N-(SiMe2CH2PPh2)2] rearranges directly to the phosphine derivative Ir(PHPhMe)[N(SiMe2CH2PPh2)2] both thermally and photolytically with no observable intermediates. Crystals of lr(CH3)PPh2[N(SiMe2CH2PPh2)2] are monoclinic with a = 13.506 (3) angstrom, b = 13.665 (3) angstrom, c = 22.816 (7) angstrom, beta = 92.35 (2)degrees, Z = 4, D(c) = 1.454 g cm-3, and space group P2(1)/c. The structure was solved by the Patterson method and refined by full-matrix least-squares procedures to R = 0.034 and R(w) = 0.037 for 3993 reflections with 1 greater-than-or-equal-to 3-sigma(I). Crystals of fac-Ir(eta-2-CH2PPh2)H[N(SiMe2CH2PPh2)21 are monoclinic with a = 9.253 (2) angstrom, b = 21.950 (5) angstrom, c = 20.081 (4) angstrom, beta = 90.74 (2)degrees, Z = 4, D(c) = 1.50 g CM-3, and space group P2(1)/c. The structure was solved by conventional heavy-atom techniques and was refined in blocks (with the Ir atom in every cycle) by using least-squares procedures down to R = 0.0356 and R(w) = 0.0370 for 4448 reflections with I greater-than-or-equal-to 3-sigma(I). Mechanistic studies showed that the formation of the cyclometalated hydride does not involve reductive transfer of the methyl and the phosphide ligands to form a phosphine complex followed by intramolecular C-H bond activation, rather C-H bond abstraction occurs first followed then by C-P bond formation. Transition-state arguments are used to rationalize the difference in the reactivity of the phenylphosphide complex for which no cyclometalated intermediate was detected.

  DOI：

  10.1021/ja00023a020