trans-[IrH((PPh2(o-C6H4CO))2)(CO)] | 870446-96-1

• 英文名称: trans-[IrH((PPh2(o-C6H4CO))2)(CO)]
• CAS: 870446-96-1；870517-91-2
• 化学式: C₃₉H₂₉IrO₃P₂
• 分子量: 799.825
• InChiKey: ZPEQLOFNHBNFBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 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：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  氯仿 、 trans-[IrH((PPh2(o-C6H4CO))2)(CO)] 以 二甲基亚砜 为溶剂， 生成 cis-[IrH((PPh2(o-C6H4CO))2)(CO)]*1.75CHCl3
  参考文献：
  名称：

  Novel Hydridoirida-β-diketones Containing Small Molecules, CO, or Ethylene:  Their Behavior in Coordinating Solvents Such as Dimethylsulfoxide or Acetonitrile

  摘要：

  New hydridoirida-beta-diketones [IrH{(PPh2(o-C6H4CO))(2)H}(CO)]ClO4 2 and [IrH{(PPh2(o-C6H4CO))(2)H}(olefin)]BF4 (olefin = C2H4, 5; 1-hexene, 10) have been prepared. These complexes may afford new diacylhydridoiridium(III) derivatives. In chloroform solution, complex 2 is in equilibrium with the deprotonated diacylhydride trans-[IrH(PPh2(o-C6H4CO))(2)(CO)] complex 3. In DMSO, deprotonation cl, 2 occurs to yield the kinetically favored product 3, which isomerizes to the thermodynamically favored complex cis-[IrH(PPh2(o-C6H4CO))(2)(CO)] 4. Reprotonation of 4 with HBF4 in chlorinated solvents gives the cation in 2. In coordinating solvents such as dimethyl sulfoxide or acetonitrile, complex 5 undergoes displacement of ethylene to afford [IrH{(PPh2(o-C6H4CO))(2)H}(L)]BF4 (L = DMSO, 7; CH3CN, 9). Complexes 5 and 7 undergo deprotonation by NEt3 to give the corresponding diacylhydrides. The ethylene complex gives only trans-[IrH(PPh2(o-C6H4CO))(2)(C2H4)] 6, while the dimethyl sulfoxide derivative affords a mixture of trans- and cis-[IrH(PPh2(o-C6H4CO))(2)(DMSO)] 8. Complex 10 shows inhibited alkene rotation around the Ir-olefin axis, All of the complexes were fully characterized spectroscopically. Single-crystal X-ray diffraction analysis was performed on complexes 3, 4, and 9. The C-13 NMR and X-ray data point to a carbenoid character in the carbon atoms bonded to iridium in the irida-beta-diketone fragment, so that it can be considered as an acyl(hydroxycarbene) moiety.

  DOI：

  10.1021/ic051219n
• 作为产物：
  描述：

  [IrH((PPh2(o-C6H4CO))2H)(CO)]ClO4*0.5CH2Cl2 在 triethylamine 作用下， 以 二氯甲烷 为溶剂， 生成 trans-[IrH((PPh2(o-C6H4CO))2)(CO)]
  参考文献：
  名称：

  Novel Hydridoirida-β-diketones Containing Small Molecules, CO, or Ethylene:  Their Behavior in Coordinating Solvents Such as Dimethylsulfoxide or Acetonitrile

  摘要：

  New hydridoirida-beta-diketones [IrH{(PPh2(o-C6H4CO))(2)H}(CO)]ClO4 2 and [IrH{(PPh2(o-C6H4CO))(2)H}(olefin)]BF4 (olefin = C2H4, 5; 1-hexene, 10) have been prepared. These complexes may afford new diacylhydridoiridium(III) derivatives. In chloroform solution, complex 2 is in equilibrium with the deprotonated diacylhydride trans-[IrH(PPh2(o-C6H4CO))(2)(CO)] complex 3. In DMSO, deprotonation cl, 2 occurs to yield the kinetically favored product 3, which isomerizes to the thermodynamically favored complex cis-[IrH(PPh2(o-C6H4CO))(2)(CO)] 4. Reprotonation of 4 with HBF4 in chlorinated solvents gives the cation in 2. In coordinating solvents such as dimethyl sulfoxide or acetonitrile, complex 5 undergoes displacement of ethylene to afford [IrH{(PPh2(o-C6H4CO))(2)H}(L)]BF4 (L = DMSO, 7; CH3CN, 9). Complexes 5 and 7 undergo deprotonation by NEt3 to give the corresponding diacylhydrides. The ethylene complex gives only trans-[IrH(PPh2(o-C6H4CO))(2)(C2H4)] 6, while the dimethyl sulfoxide derivative affords a mixture of trans- and cis-[IrH(PPh2(o-C6H4CO))(2)(DMSO)] 8. Complex 10 shows inhibited alkene rotation around the Ir-olefin axis, All of the complexes were fully characterized spectroscopically. Single-crystal X-ray diffraction analysis was performed on complexes 3, 4, and 9. The C-13 NMR and X-ray data point to a carbenoid character in the carbon atoms bonded to iridium in the irida-beta-diketone fragment, so that it can be considered as an acyl(hydroxycarbene) moiety.

  DOI：

  10.1021/ic051219n

文献信息

• Reactivity of hydridoirida-β-diketones with bases: the selective formation of new di-μ-acyl-μ-hydridodiiridium(iii) or dihydridoirida-β-diketone complexes and heterometallic Ir(iii)–Rh(i) derivatives
  作者：Francisco Acha、Roberto Ciganda、María A. Garralda、Ricardo Hernández、Lourdes Ibarlucea、Elena Pinilla、M. Rosario Torres

  DOI：10.1039/b803488e

  日期：——

  The hydridoirida-β-diketone [IrHCl(PPh2(o-C6H4CO))2H}] (1a) reacts with bases such as KOH or NaHCO3 in methanol to undergo dehydrodechlorination and acyl-bridge formation affording [Ir2H2(PPh2(o-C6H4CO))2(μ-PPh2(o-C6H4CO))2] (2) with two acylphosphine chelate-bridging ligands, in a head-to-tail disposition, and terminal hydrides. The acyl bridges can be broken by pyridine, PPh3, CO or dimethylsulfoxide affording selectively mononuclear diacylhydrido neutral derivatives [IrH(PPh2(o-C6H4CO))2L] (3–6). 1a reacts with KOH or NaHCO3 in refluxing methanol to afford a novel dihydridoirida-β-diketone [IrH2(PPh2(o-C6H4CO))2H}] (7), via dehydrodechlorination to afford 2, which then undergoes hydrogenation and protonation. The reaction of 1a with NEt3 affords 2 and [NHEt3]Cl. Further reaction affords [Ir2(μ-H)μ-PPh2(o-C6H4CO)}2(PPh2(o-C6H4CO))2]+ (8), with two acylphosphine chelate-bridging ligands and a bridging hydride. Neutral or cationic hydridoirida-β-diketone complexes react with [Rh(cod)(OMe)]2 (cod = 1,5-cyclooctadiene) to afford hydridoirida-β-diketonaterhodium(I) complexes [IrHCl(μ-PPh2(o-C6H4CO))2Rh(cod)] (9) or [IrHL(μ-PPh2(o-C6H4CO))2Rh(cod)]ClO4 (L = py, 10; CO, 11), respectively that isomerise to the thermodynamically stable isomers of [IrCl(PPh2(o-C6H4CO))(μ-H))(μ-PPh2(o-C6H4CO))Rh(cod)] (12) or [Ir(py)(PPh2(o-C6H4CO))(μ-H))(μ-PPh2(o-C6H4CO))Rh(cod)]ClO4 (13). The reaction of 7 with [Rh(cod)(OMe)]2 affords [Ir(PPh2(o-C6H4CO))2(μ-H)2Rh(cod)] (14). All the complexes were fully characterised spectroscopically. Single-crystal X-ray diffraction analysis was performed on 2, 4, 7, [8]ClO4 and 9.

  铱铱δ-二酮[IrHCl(PPh2(o-C6H4CO))2H}]（1a）在甲醇中与 KOH 或 NaHCO3 等碱反应，发生脱氢脱氯反应并形成酰基桥，生成带有两个酰基膦螯桥配体的[Ir2H2(PPh2(o-C6H4CO))2(δ-PPh2(o-C6H4CO))2]（2）、和末端氢化物。酰基桥可被吡啶、PPh3、CO 或二甲基亚砜打断，从而产生选择性的单核二酰肼中性衍生物 [IrH(PPh2(o-C6H4CO))2L] (3â6)。1a 与 KOH 或 NaHCO3 在回流甲醇中反应，生成新型二氢铱-δ-二酮[IrH2(PPh2(o-C6H4CO))2H}](7)，通过脱氢脱氯生成 2，然后进行氢化和质子化反应。1a 与 NEt3 反应生成 2 和 [NHEt3]Cl。进一步反应得到[Ir2(δ-H)δ-PPh2(o-C6H4CO)}2(PPh2(o-C6H4CO))2]+ (8)，其中有两个酰基膦螯桥配体和一个桥氢化物。中性或阳离子铱铱δ-二酮配合物与 [Rh(cod)(OMe)]2 （cod = 1、5-环辛二烯）反应，得到铱铱δ-二酮钠（I）络合物 [IrHCl(δ-PPh2(o-C6H4CO))2Rh(cod)] (9) 或 [IrHL(δ-PPh2(o-C6H4CO))2Rh(cod)]ClO4 (L = py、10；CO，11），分别异构成热力学稳定的异构体[IrCl(PPh2(o-C6H4CO))(δ-H))(δ-PPh2(o-C6H4CO))Rh(cod)]（12）或[Ir(py)(PPh2(o-C6H4CO))(δ-H))(δ-PPh2(o-C6H4CO))Rh(cod)]ClO4（13）。7 与 [Rh(cod)(OMe)]2 反应生成 [Ir(PPh2(o-C6H4CO))2(δ-H)2Rh(cod)]（14）。所有复合物都经过了全面的光谱表征。对 2、4、7、[8]ClO4 和 9 进行了单晶 X 射线衍射分析。