Ir(H)2(OTf)(P(t)Bu2Ph)2 | 195607-97-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: Ir(H)2(OTf)(P(t)Bu2Ph)2
• CAS: 195607-97-7
• 化学式: C₂₉H₄₈F₃IrO₃P₂S
• 分子量: 787.927
• InChiKey: GEGOTXSJSVGSGI-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Ir(H)2(OTf)(P(t)Bu2Ph)2 在 ethylene 作用下， 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  Fluoro-Ligand Promotion of C−H Activation

  摘要：

  Ethylene dehydrogenates Ir(H)(2)FL(2) (L = P-t-Bu(2)Ph) to give the metalated species 1 and 2. These metalated species catalyze the exchange of deuterium from C6D6 to ethylene, and to (t)Bu and ortho phenyl sites of coordinated L. This exchange is proposed to benefit from pi-donation from F to Ir.

  DOI：

  10.1021/om9605488
• 作为产物：
  描述：

  bis(di-tert-butyl(phenyl)-l5-phosphaneyl)(isothiocyanato)iridium(V) hydride 以 氘代氯仿 、 氘代苯 为溶剂， 生成 Ir(H)2(OTf)(P(t)Bu2Ph)2
  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

• HX elimination from Ir(H)2X(PBu2tPh)2 promoted by CO coordination: assessment of X ligand influence
  作者：Alan C. Cooper、John C. Bollinger、John C. Huffman、Kenneth G. Caulton

  DOI：10.1039/a800525g

  日期：——

  crystalline [Ir(H)2(CO)2(PBu2tPh)2][SiF5] and [Ir(CO)2(PBu2tPh)2][SiF5]·C6D6, both characterized by X-ray diffraction. The latter, although approximately square planar, has a C–Ir–C angle of only 162.7°. Crystallographic data (Pc at -165 °C) for [Ir(H)2(CO)2(PBu2tPh)2][SiF5], a=8.293(2), b=12.462(5), c=16.333(7) Å, β=98.21(2)° with Z=2. Crystallographic data (P21/n at -172 °C) for [Ir(CO)2(PBu2tPh)2][SiF5]·C6D6

  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
• <i>tert</i>-Butyl Is Superior to Phenyl as an Agostic Donor to 14-Electron Ir(III)
  作者：Alan C. Cooper、William E. Streib、Odile Eisenstein、Kenneth G. Caulton

  DOI：10.1021/ja970763v

  日期：1997.9.1