| 61663-66-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 61663-66-9
• 化学式: C₂₈H₄₈IIrP₂
• 分子量: 765.761
• InChiKey: JXMQZYNZIVBSLG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  9.13
• 重原子数：
  32.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  、 一氧化碳 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  CO配位促进从Ir（H）2 X（PBu 2 t Ph）2去除HX ：X配体影响的评估

  摘要：

  配位不饱和配合物Ir（H）2 X（PBu 2 t Ph）2 [X = Cl，Br，I，N 3，N C NSiMe 3，NHC（O）CH 3，OC（O）CF 3，OSO 2 CF 3，OC（O）CH 3，SPh，OPh，F]均在混合时间内在芳烃溶剂中反应以结合一氧化碳。这些CO加合物随后还原性消除HX的反应性取决于配体pπ轨道和金属dπ轨道之间的填充-排斥反应所引起的固有不稳定程度。这种不稳定不是当X = Cl，Br，I，N 3，N C NSiMe 3，NHC（O）CH 3或OC（O）CF 3时，足以促进HX的损失。当X = OC（O）CH 3或SPh时，形成亚稳的CO加合物，最终失去HX。含有OPh或F的配合物在与CO反应后迅速失去HX。不寻常的铱（I）配合物IrH（CO）2（PBu 2 t Ph）和IrH（CO）（PBu 2 t Ph）2已通过多核NMR进行了表征和红外光谱。Ir（H）2（F）（PBu

  DOI：

  10.1039/a800525g
• 作为产物：
  描述：

  碘代三甲硅烷 、 Ir(H)2F(P(t)Bu2Ph)2 以 甲苯 为溶剂， 以96%的产率得到
  参考文献：
  名称：

  Silyl reagents (Me3Si-X) efficiently transfer X to Ir(H)2F(PtBuP2Ph)2

  摘要：

  Me3Si-X reagents react to completion at 25 degrees C in a short time to convert Ir(H)(2)FL2 (L = (PBu2Ph)-Bu-t) to Ir(H)(2)XL2. This involves formation of Ir-O, Ir-N, Ir-I, Ir-S and Ir-C(sp) bonds. Products include some pi(2)-X ligands such as carboxylate and acetamide, NHC(O)CH3. The acetamide is shown to be pi(2) in the solid state and in solution, but readily rearranges, by a transition state with Ir-O bond cleavage, to effect site exchange of the two inequivalent hydrides. The same synthetic approach succeeds for the more crowded metallated species and these reactions are shown to fail when F is replaced by Cl in the iridium reagent. Unsaturation at Ir is suggested to be central to the mechanism of these F/X transposition reactions. (C) 1998 Elsevier Science S.A.

  DOI：

  10.1016/s0020-1693(97)05851-9

文献信息

• Some iridium hydride and tetrahydroborate complexes with bulky tertiary phosphine ligands
  作者：H. David Empsall、Eileen M. Hyde、Eric Mentzer、Bernard L. Shaw、Michael F. Uttely

  DOI：10.1039/dt9760002069

  日期：——

  tetrahydroborate to give complexes [Ir(BH4)H2(PRBut2)2]. These are non-fluxionbl and have been characterized by 1H, 31P, and 11B n.m.r. spectroscopy. The complexes [Ir(BD4)H2(PBut3)2] and [Ir(BD4)DH(PMeBut2)2] have also been prepared by Li[BD4] reductions. The complex [Ir(BH4)H2(PMeBut2)2] decomposes slowly in deuteriotoluene to [IrH5(PMeBut2)2] but [Ir(BH4)H2(PButt3)2] seems to be indefinitely stable

  三氯化铱与丙-2-醇中的PBu t 2 Ph或PBu t 3（L）反应生成五坐标二氢化物[IrClH 2 L 2 ]。配合物[IrClH 2（PBu t 2 Ph）2 ]与碘化钠反应生成[IrH 2 I（PBu t 2 Ph）2 ]或与一氧化碳反应生成[Ir（CO）ClH 2（PBu t 2）Ph ）2 ]。与二氢和丙-2-酸钠一起，[IrClH 2 L 2 ]得到相应的五氢化物[IrH 5 L 2]。的类型的氢化物[的IrCl 3- X ħ X（PRBu吨2）2 ]（一）X = 1，R = Me或（b）X = 2，R =卜吨与钠反应四氢得到配合物的[Ir （BH 4）H 2（PRBu t 2）2 ]。这些是非fluxionbl，并已通过1 H，31 P和11 B nmr光谱表征。络合物[Ir（BD 4）H 2（PBu t 3）2]和[Ir（BD 4）DH（PMeBu t 2）2 ]也通过Li
• Poulton, Jason T.; Hauger, Bryan E.; Kuhlman, Roger L., Inorganic Chemistry, 1994, vol. 33, # 15, p. 3325 - 3330
  作者：Poulton, Jason T.、Hauger, Bryan E.、Kuhlman, Roger L.、Caulton, Kenneth G.

  DOI：——

  日期：——
• Identification of an elusive catalyst: IrH(η2-C6H4PtBu2) (Cl)(PtBu2Ph) as a precursor for C=C bond migration
  作者：Alan C. Cooper、Kenneth G. Caulton

  DOI：10.1016/s0020-1693(96)05249-8

  日期：1996.10

  The catalytic isomerization of allylbenzene to cis/trans-beta-Me styrene in solutions containing Ir(III) hydride halide, hydride hydroxide and hydride alkoxide Ir(H)(2)X(P(t)Bu(2)Ph)(2)(X=F, Cl, Br, I, OH, OCH2CF3) is described. Large variations in isomerization rate (k(obs)) are found to correlate with the electron donating ability (pi + sigma) of the X ligand: the rate is enhanced by more effective donation by the X Ligands. A number of kinetic studies and phosphine exchange experiments utilizing a deuterium labeled phosphine, P(t)Bu(2)(d(5))Ph, indicate that the active isomerization catalyst is a 14-valence-electron Ir(III) species derived from the ortha-metallated complex, IrH(eta(2)-C(6)H(4)P(t)Bu(2))(X) (P(t)Bu(2)Ph), by phosphine dissociation. Using IrH(eta(2)-C(6)H(4)P(t)Bu(2)) (Cl)(P(t)Bu(2)Ph) as a catalyst precursor, the catalytic isomerization of alpha,alpha-d(2)-allylbenzene in the presence of an excess of 4-allyl anisole has yielded primarily d(1)-cis/trans-beta-Me styrene, which confirms that the isomerization proceeds via an insertion-elimination mechanism of a metal hydride bond.