[Ir(H)₂(PPh₃)₂(Me₂CO)₂]PF₆ | 73209-98-0

• 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: [Ir(H)₂(PPh₃)₂(Me₂CO)₂]PF₆
• 英文别名: [Ir(hydrido)2(acetone)2(triphenylphosphine)2](PF6)；[IrH2(acetone)2(PPh3)2](PF6)
• CAS: 73209-98-0
• 化学式: C₄₂H₄₄IrO₂P₂*F₆P
• 分子量: 979.942
• InChiKey: GNIBGHDZLAHDHD-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：

  [Ir(H)₂(PPh₃)₂(Me₂CO)₂]PF₆ 在 H₂ 、 CO 作用下， 以 氯仿 、 1,2-二氯乙烷 为溶剂， 生成 dicarbonylbis(triphenylphosphine)dihydridoiridium hexafluorophosphate
  参考文献：
  名称：

  HDS模型系统。2,3-二氢噻吩在铱上噻吩均匀氢化为四氢噻吩的中间体

  摘要：

  Thermolysis of the bis(thiophene) (T) dihydride L(PPh3)2Ir(H)2(eta1-SC4H4)2]PF6 (1) in 1,2-dichloroethane at 80-degrees-C gives the thioallyl complex [(PPh3)2IrH(eta4-SC4H5)]PF6 (2) by a stereospecific endo migration of one of the coordinated hydrides. Reaction of the thioallyl complex with H-2 under mild conditions yields the bis(tetrahydrothiophene) (THT) dihydride [(PPh3)2Ir(H)2(eta1-SC4H8)2]PF6 (3) plus the pentahydride [{(PPh3)2IrH}2(mu2-H)3]PF6 (4); if the hydrogenation is carried out in the presence of excess T, complex 3 is obtained exclusively. Interaction of 2 with CO at room temperature produces the two novel isomeric derivatives [(PPh3)2Ir(H)(CO)(eta2-C5,S-SC4H5)]PF6 (7) and [(PPh3)2Ir(H)(CO)(eta2-C3,S-SC4H5)]PF6 (8) in a 5:1 ratio, which do not interconvert from -50 to +80-degrees-C; longer reaction times (24 h, 25-degrees-C) or higher temperatures (3 h, 50-degrees-C) result in quantitative conversion of the complex to [(PPh3)2-Ir(CO)3]PF6, with concomitant liberation of 2,5-dihydrothiophene (2,5-DHT) and 2,3-DHT in a 5:1 ratio. Reaction of 2 with 2,5-DHT under H-2 at 80-degrees-C produces the new bis(2,5-DHT) dihydride complex [(PPh3)2Ir(H)2(eta1-2,5-SC4H6)2]PF6 (5), whereas the analogous reaction with 2,3-DHT results in hydrogenation to yield the bis(THT) dihydride derivative 3. Complex 5 and its 2,3-DHT analog [(PPh3)2Ir(H)2(eta1-2,3-SC4H6)2]PF6 (6) may also be prepared by displacement of coordinated acetone in [(PPh3)2Ir(H)2(Me2CO)2]PF6(5) by the appropriate ligand. Complex 5 does not react with H-2 at 80-degrees-C, whereas 6 is readily transformed into 3 under analogous conditions. Interaction of 2 with syngas results in the production of 7 and 8, together with free 2,5-DHT and 2,3-DHT, plus small amounts of [(PPh3)2Ir(H)2(CO)(eta1-SC4H8)]PF6 (10) and [(PPh3)2Ir(H)2(CO)2]PF6(11). These combined results clearly establish that only the 2,3-DHT isomer is an intermediate in the homogeneous hydrogenation of T to THT (via the isolated thioallyl (2) and hydrido-eta2-C,S (8) intermediates) with this Ir system, a result of relevance in connection with the HDS mechanisms. The THT complex 10 crystallizes in monoclinic space group P2(1) (No. 4) with a = 9.563(4) angstrom, b = 23.201(4) angstrom, c = 11.221(2) angstrom, beta = 97.870 (2), Z = 2, and V = 2466.16 A3. The structure of the complex cation consists of a distorted octahedron with mutually cis-hydrides, cis-THT, and CO and trans-PPh3 ligands.

  DOI：

  10.1021/om00014a050
• 作为产物：
  描述：

  氢气 、 丙酮 、 [(cod)Ir(PPh₃)₂]PF₆ 以 丙酮 为溶剂， 生成 [Ir(H)₂(PPh₃)₂(Me₂CO)₂]PF₆
  参考文献：
  名称：

  Synthesis, characterization, and X-ray structures of three iridium(III)-hydrido-cyclometallated-imine complexes, including the first reported hydrido-(η¹-imine)-Ir complex

  摘要：

  顺式、反式、顺式-[Ir(H)2(PPh3)2(solv)2]PF6（solv = MeOH 或 Me2CO）与亚胺 HN=CPh2、(o-HOC6H4)C(Me)=NCH2Ph、和 PhC(H)=N(p-F-C6H4)在 MeOH 或丙酮中，在氩气条件下生成[IrH{NH=C(Ph)(o-C6H4)}(NH=CPh2)(PPh3)2]PF6 (3) 复合物、[IrH{PhCH2N=C(Me)(o-C6H3OH)}(solv)(PPh3)2]PF6 (其中 solv = MeOH (4) 或 Me2CO (4a))，以及 [IrH{N(p-F-C6H4)=CH(o-C6H4)}(Me2CO)(PPh3)2]PF6 (5a)。亚胺 (C6F5)C(H)=NPh 对 Ir 前体没有反应。3、4-2MeOH 和 5a-1/2Me2CO 的 X 射线结构显示，一个 η2-N,C 亚胺分子通过 N 原子和一个正金属 C 原子配位。络合物 3 同时含有一个正金属化亚胺和一个 η1- 亚胺，是第一个具有结构特征的氢化物-（η1-亚胺）-Ir 络合物。关键词：铱、氢化物配合物、亚胺、氟亚胺、膦配合物、正金属化、晶体学、核磁共振光谱。

  DOI：

  10.1139/v07-153

文献信息

• Syntheses and structural characterizations of novel mono- and dinuclear iridium hydrido complexes with polydentate nitrogen donor ligands
  作者：Masahiko Maekawa、Toshie Minematsu、Hisashi Konaka、Kunihisa Sugimoto、Takayoshi Kuroda-Sowa、Yusaku Suenaga、Megumu Munakata

  DOI：10.1016/j.ica.2004.03.052

  日期：2004.9

  and dinuclear Ir hydrido complexes with polydentate nitrogen ligands, [Ir(H)2(PPh3)2(tptz)]PF6 (1), [Ir2(H)4(PPh3)4(tptz)](PF6)2 · 2H2O (2 · 2H2O), [Ir(H)2(PPh3)2(tppz)]BF4 (3), [Ir2(H)4(PPh3)4(tppz)](BF4)2 (4) and [Ir2(H)4(PPh3)4(bted)](BF4)2 · 6CHCl3 (5 · 6CHCl3), were systematically prepared by the reactions of the precursor Ir hydrido complex [Ir(H)2(PPh3)2(Me2CO)2]X (X=PF6 and BF4) with 2,4,6-tris(2-pyridyl)-1

  新的五种具有多齿氮配体的单核和双核Ir氢化物，[Ir（H）2（PPh 3）2（tptz）] PF 6（1），[Ir 2（H）4（PPh 3）4（tptz） ]（PF 6）2  ·2H 2 O（2  ·2H 2 O），[Ir（H）2（PPh 3）2（tppz）] BF 4（3），[Ir 2（H）4（PPh 3）4（tppz）]（BF 4）2（4）和[Ir 2（H）4（PPh 3）4（bted）]（BF 4）2  ·6CHCl 3（5  ·6CHCl 3），是通过前体Ir氢化物络合物[Ir （H）2（PPh 3）2（Me 2 CO）2 ] X（X = PF 6和BF 4）与2,4,6-三（2-吡啶基）-1,3,5-三嗪（tptz） ，2,3,5,6-四（2-吡啶基）吡嗪（tppz）和1,4-双（2,2 '：6 '，2 '' -三吡啶-4 '（固态）和（固态）表征了它们的结构和性质。具有结晶多齿
• Syntheses and reactivities of hydrosulfido- or sulfido-bridged heterobimetallic complexes containing Group 6 and Group 9 metals
  作者：Hiroko Kato、Hidetake Seino、Yasushi Mizobe、Masanobu Hidai

  DOI：10.1039/b108227m

  日期：2002.3.26

  Reactions of [Cp2M(SH)2] (M = Mo 1, W 2) with one equiv of [IrH2(PPh3)2(Me2CO)2][PF6] in acetone at room temperature under 1 atm of H2 afforded the hydrosulfido–hydrido complexes [Cp2M(μ-SH)2IrH2(PPh3)2][PF6] (M = Mo 4, W 5), whereas those of 1 and 2 with [RhH2(PPh3)2(Me2CO)(EtOH)][PF6] 6 resulted in the formation of [Cp2Mo(μ-SH)2Rh(PPh3)2][PF6] 7 and [Cp2W(μ-S)2Rh(PPh3)2][PF6] 8. X-Ray analyses have been undertaken to clarify the detailed structure of [Cp2Mo(μ-SH)2IrH2(PPh3)2][BPh4] derived from 4 along with 7 and 8. Bimetallic complexes 4, 5, 7, and 8 catalysed the hydrogenation of alkynes such as 1-octyne and tert-butyl propiolate at room temperature under 1 atm of H2, yielding 1-octene and tert-butyl acrylate as the major products, respectively. In both reactions, the Mo–Rh complex 7 showed the highest catalytic activity, although even the reactions using 7 are much slower than those catalyzed by the mononuclear Rh complex 6.

  室温下，在 1 个大气压的 H2 条件下，[Cp2M(SH)2]（M = Mo 1，W 2）与等当量的[IrH2(PPh3)2(Me2CO)2][PF6]在丙酮中发生反应，生成了氢硫氢配合物[Cp2M(μ-SH)2IrH2(PPh3)2][PF6]（M = Mo 4，W 5）、W 5），而 1 和 2 与 [RhH2(PPh3)2(Me2CO)(EtOH)][PF6] 6 生成 [Cp2Mo(μ-SH)2Rh(PPh3)2][PF6] 7 和 [Cp2W(μ-S)2Rh(PPh3)2][PF6] 8。通过 X 射线分析，阐明了由 4 以及 7 和 8 生成的[Cp2Mo(μ-SH)2IrH2(PPh3)2][BPh4]的详细结构。双金属配合物 4、5、7 和 8 可在室温、1 atm 的 H2 下催化 1-辛炔和丙炔酸叔丁酯等炔烃的氢化反应，主要产物分别为 1-辛烯和丙烯酸叔丁酯。在这两个反应中，Mo-Rh 复合物 7 显示出最高的催化活性，尽管使用 7 的反应也比单核 Rh 复合物 6 催化的反应慢得多。
• Syntheses and structural characterizations of mononuclear Ir(III) hydride complexes with 2,2′:6′,2″-terpyridine in the κ2N,N' and κ3N,N',N″ coordination modes
  作者：Masahiko Maekawa、Kota Terada、Shoki Oda、Kunihisa Sugimoto、Takashi Okubo、Takayoshi Kuroda-Sowa

  DOI：10.1016/j.ica.2020.119962

  日期：2021.1

  Abstract The reactions of [Ir(H)2(PPh3)2(Me2CO)2]X (X = PF6, BF4) with terpy in CHCl3, Me2CO and CH2Cl2 under Ar afforded three novel Ir(III)-hydride complexes 1 - 3 by the choices of solvents and anions. Ir(III)-terpy hydride complexes [Ir(H)2(PPh3)2(terpy-κ2N,N')]PF6•CHCl3 (1) and [Ir(H)2(PPh3)2(terpy-κ2N,N')]BF4•Me2CO (2) with two cis hydride atoms, two PPh3 and terpy-κ2N,N' possess a octahedral

  摘要在氩气中，[Ir（H）2（PPh3）2（Me2CO）2] X（X = PF6，BF4）与叔丁基在CHCl3，Me2CO和CH2Cl2中反应生成了三种新型的Ir（III）-氢化物配合物1-3通过选择溶剂和阴离子。Ir（III）-叔氢化物[Ir（H）2（PPh3）2（terpy-κ2N，N'）] PF6• （1）和[Ir（H）2（PPh3）2（terpy-κ2N，N） '）]具有两个顺式氢化物原子，两个PPh3和terpy-κ2N，N'的 •Me2CO（2）具有八面体N2P2H2配位模式，而类似钳状的Ir（III）-叔氢化物络合物[Ir（H）（ PPh3）2（terpy-κ3N，N'，N''）]（ ）2•2 } 2（3）具有一个氢化物原子，两个PPh3和terpy-κ3N，N'，N''具有八面体N3P2H配位模式。1 H NMR分析显示三种Ir（III）-叔氢化
• Reactions of dienes with the ion [Ir(PPh3)2(OCMe2)2H2]+ : a kinetic and mechanistic study of complex formation and diene hydrogenation
  作者：Oliver W. Howarth、Colin H. McAteer、Peter Moore、George E. Morris

  DOI：10.1039/dt9840001171

  日期：——

  cyclohexa-1,3- or -1,4-diene react with (1) to give highly fluxional allyl–hydride species which feature an aliphatic C–H ⋯ IrIII interaction. Variable-temperature 1H and 31P n.m.r., and 1H spin-saturation transfer experiments reveal a facile reversible hydrogen-transfer process between metal and hydrocarbon ligand which occurs via a C–H ⋯ IrIII interaction.

  停止流动的nmr揭示了环八-1,5-二烯（cod）和双环[2.2.1]庚2,5-二烯（降冰片二烯，nbd）与离子[Ir（ PPh 3）2（OCMe 2）2 H 2 ] +（1）。[Ir（PPh 3）2（二烯）H 2 ] +离子是最先形成的产物。通过1 H和31 P nmr光谱已观察到所有三种[Ir（PPh 3）2（nbd）H 2 ] +异构体的相互转化。这些物质进一步反应生成[Ir（PPh 3）2（nbd）] +（2），可以通过消除H 2或通过配位的nbd的氢化形成双环[2.2.1]庚-2-烯（降冰片烯，nbe）来实现。停止流式分光光度法揭示了在nbd的氢化或氘化期间形成（2）的显着逆动力学同位素效应。提出了一种涉及二烯-二氢化物和烷基-氢化物之间平衡的机理。二烯2,3-二甲基丁二烯和环己-1,3-或-1,4-二烯与（1）反应生成高通量的烯丙基氢化物，其特征是具有脂肪族C–H⋯Ir III相互作用。可变温度1
• Heterometallic Ag ^I –Ir ^III Hydride Coordination Polymers Bridged by Ir ^III Metalloligands
  作者：Masahiko Maekawa、Yukimi Kubo、Kunihisa Sugimoto、Takashi Okubo、Takayoshi Kuroda‐Sowa、Megumu Munakata

  DOI：10.1002/ejic.201500996

  日期：2016.1

  [Ir(H)2(PPh3)2(pprd)]BF4·2CHCl3 (1), [Ir(H)2(PPh3)2(Me2bpm)]BF4·CHCl3 (2), [Ir(H)2(PPh3)2(Me2bpm)]PF6·CHCl3}4 (3), [Ir(H)2(PPh3)2(biqz)]BF4·2CHCl3 (4), and [Ir(H)2(PPh3)2(biqz)]PF6 (5), have been prepared by reaction of [Ir(H)2(PPh3)2(Me2CO)2]X (X = BF4 or PF6) with 4-(2-pyridyl)pyrimidine (pprd), 6,6′-dimethyl-4,4′-bipyrimidine (Me2bpm), or 4,4′-biquinazoline (biqz). Subsequently, three novel heterometallic

  一种含有不饱和氮配位点的新型 IrIII 金属配体 [Ir(H)2(PPh3)2(pprd)] ·2 (1), [Ir(H)2(PPh3)2(Me2bpm)] · CHCl3 (2), [Ir(H)2(PPh3)2(Me2bpm)]PF6· }4 (3), [Ir(H)2(PPh3)2(biqz)] ·2 (4),和 [Ir(H)2(PPh3)2(biqz)]PF6 (5)，已通过 [Ir(H)2(PPh3)2(Me2CO)2]X (X = BF4 或 PF6) 与4-(2-吡啶基)嘧啶 (pprd)、6,6'-二甲基-4,4'-联嘧啶 (Me2bpm) 或 4,4'-联喹唑啉 (biqz)。随后，三种新型的异金属 AgI-IrIII 氢化物配位聚合物，[Ir(H)2(μ-pprd)(PPh3)2Ag(η-CF3COO)] ·Me2CO}n (6)，[Ir(H)2