| 84074-31-7

• CAS: 84074-31-7
• 化学式: C₃₁H₃₆IrNOP₂Si₂
• 分子量: 748.971
• InChiKey: FZNDIRPAVAHEAH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• 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：

  在 methyl iodide 作用下， 以 甲苯 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  Fryzuk, Michael D.; MacNeil, Patricia A.; Rettig, Steven J., Organometallics, 1986, vol. 5, # 12, p. 2469 - 2476

  摘要：

  DOI：
• 作为产物：
  描述：

  以 苯 为溶剂， 生成
  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

文献信息

• Synthesis and reactivity of the coordinatively unsaturated methylene complex Ir:CH2[N(SiMe2CH2PPh2)2]
  作者：Michael D. Fryzuk、Xiaoliang Gao、Kiran Joshi、Patricia A. MacNeil、Roberta L. Massey

  DOI：10.1021/ja00076a016

  日期：1993.11

  The reactions of the coordinatively unsaturated iridium methylene complex IrCH 2 [N(SiMe 2 CH 2 PPh 2 ) 2 ] are described. This methylene complex is prepared by the reaction of 2 equiv of KOBu t with the methyl iodide derivative Ir(CH 3 )I[N(SiMe 2 CH 2 PPh 2 ) 2 ] in toluene; the extra equivalent of KOBu t serves to coordinate the HOBu t that is produced as the precipitate KOBu t -HOBu t . The reaction

  描述了配位不饱和铱亚甲基配合物IrCH 2 [N(SiMe 2 CH 2 PPh 2 ) 2 ] 的反应。该亚甲基配合物是通过 2 当量的 KOBu t 与甲基碘衍生物 Ir(CH 3 )I[N(SiMe 2 CH 2 PPh 2 ) 2 ] 在甲苯中反应制备的；KOBu t 的额外等价物用于协调作为沉淀物KOBu t -HOBu t 产生的HOBu t 。H 2 与亚甲基络合物的反应通过一系列氧化加成和迁移插入步骤生成三氢化胺 IrH 3 [HN(SiMe 2 CH 2 PPh 2 ) 2 ]；三氢化物衍生物在后处理时失去 H 2 以生成二氢化铱 (III) IrH 2 [N(SiMe 2 CH 2 PPh 2 ) 2 ]