bis(di-tert-butyl(phenyl)-l5-phosphaneyl)iridium(V) fluoride dihydride | 185250-10-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(di-tert-butyl(phenyl)-l5-phosphaneyl)iridium(V) fluoride dihydride
• CAS: 185250-10-6
• 化学式: C₂₈H₄₈FIrP₂
• 分子量: 657.855
• InChiKey: OIMAHGFKLQLPCJ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  8.66
• 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

• 作为产物：
  描述：

  、 cesium fluoride 在 18-冠醚-6 作用下， 以 苯 为溶剂， 生成 bis(di-tert-butyl(phenyl)-l5-phosphaneyl)iridium(V) fluoride dihydride
  参考文献：
  名称：

  Hauger, Bryan E.; Gusev, Dmitry; Caulton, Kenneth G., Journal of the American Chemical Society, 1994, vol. 116, # 1, p. 208 - 214

  摘要：

  DOI：

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
• 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.
• Silyl reagents (Me3Si-X) efficiently transfer X to Ir(H)2F(PtBuP2Ph)2
  作者：Alan C. Cooper、John C. Huffman、Kenneth G. Caulton

  DOI：10.1016/s0020-1693(97)05851-9

  日期：1998.4

  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.
• Fluoro-Ligand Promotion of C−H Activation
  作者：Alan C. Cooper、Kirsten Folting、John C. Huffman、Kenneth G. Caulton

  DOI：10.1021/om9605488

  日期：1997.2.1

  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.
• <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