bis(μ-acetato)dicarbonyldichlorodiiridium(II) | 259672-87-2

• 英文名称: bis(μ-acetato)dicarbonyldichlorodiiridium(II)
• 英文别名: bis(μ-acetato)dichlorodicarbonyldiiridium(II)；[Ir2(μ-O2CMe)2Cl2(CO)2]
• CAS: 259672-87-2
• 化学式: C₆H₆Cl₂Ir₂O₆
• 分子量: 629.456
• InChiKey: HHQQSEALQMBREH-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  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：

  吡啶 、 bis(μ-acetato)dicarbonyldichlorodiiridium(II) 以 吡啶 、 甲苯 为溶剂， 以77%的产率得到bis(pyridine)bis(μ-acetato)dichlorodicarbonyldiiridium(II)
  参考文献：
  名称：

  铱（II）双核配合物的一步合成。双（μ-乙酰基）二羰基二氯二铱（II）配合物的制备，结构和性能†

  摘要：

  A双（μ-乙酸基）dicarbonyldichlorodiiridium（II）复合物，的[Ir 2（μ-O 2 CME）2氯2（CO）2 ] 1，通过H的一步反应制备2的IrCl 6与梅科2栗在O 2下，在乙酸和乙酸酐的混合溶剂中。将1溶解在各种连接溶剂中，得到[Ir 2（µ-O 2 CMe）2 Cl 2（CO）2 L 2]（L ＝ MeCN 2，dmso 3，py 4或4-异丙基吡啶5）。2、3和4的晶体结构测定分别得出Ir-Ir距离为2.569（1），2.5980（5）和2.5918（5）Å，这在报告的Ir II –Ir II单键距离范围内。2、4和5的CV在1.30 V，0.97和0.94 V vs.的E 1/2处显示出单电子准可逆氧化波。Fc + -Fc分别。复合物3在dmso的潜在窗口中没有CV响应。4和5的电解或辐射单电子氧化产生了它们的阳离子自由基，其中的冷冻溶液给出了准轴向对称的ESR光谱。所述克张量克1

  DOI：

  10.1039/a907776f
• 作为产物：
  描述：

  hydrogen hexachloroiridate hydrate 、 lithium acetate 在 O₂ 作用下， 以 乙酸酐 、 溶剂黄146 为溶剂， 以30%的产率得到bis(μ-acetato)dicarbonyldichlorodiiridium(II)
  参考文献：
  名称：

  铱（II）双核配合物的一步合成。双（μ-乙酰基）二羰基二氯二铱（II）配合物的制备，结构和性能†

  摘要：

  A双（μ-乙酸基）dicarbonyldichlorodiiridium（II）复合物，的[Ir 2（μ-O 2 CME）2氯2（CO）2 ] 1，通过H的一步反应制备2的IrCl 6与梅科2栗在O 2下，在乙酸和乙酸酐的混合溶剂中。将1溶解在各种连接溶剂中，得到[Ir 2（µ-O 2 CMe）2 Cl 2（CO）2 L 2]（L ＝ MeCN 2，dmso 3，py 4或4-异丙基吡啶5）。2、3和4的晶体结构测定分别得出Ir-Ir距离为2.569（1），2.5980（5）和2.5918（5）Å，这在报告的Ir II –Ir II单键距离范围内。2、4和5的CV在1.30 V，0.97和0.94 V vs.的E 1/2处显示出单电子准可逆氧化波。Fc + -Fc分别。复合物3在dmso的潜在窗口中没有CV响应。4和5的电解或辐射单电子氧化产生了它们的阳离子自由基，其中的冷冻溶液给出了准轴向对称的ESR光谱。所述克张量克1

  DOI：

  10.1039/a907776f

文献信息

• Preparation and structure of bis(μ-acetato)dichlorodicarbonyldiiridium(II) complexes with Group 15 ligands and ESR and density functional theory studies of electronic structure of their cationic radicals
  作者：Naohiro Kanematsu、Masahiro Ebihara、Takashi Kawamura

  DOI：10.1016/s0020-1693(01)00615-6

  日期：2001.10

  bis(mu -Acetato)dichlorodicarbonyldiiridium(II) complexes with Group 15 compounds as axial ligands, [Ir-2(mu -O2CMe)(2)Cl-2(CO)(2)L-2] (L = PPh3: 1, PCy3: 2, P(OPh)(3): 3, AsPh3: 4, SbPh3: 5) were synthesized. The Ir-Ir distances of complexes 2-5 (2.6200(9)-2.6936(7) Angstrom) were longer than those of the complexes with MeCN, py or dmso ligands at the axial sites. Cyclic voltammograms of 1 - 5 show a chemically reversible one-electron oxidation wave of which E-1/2 (vs. Fc(+) - Fc) values were between 0.22 for 2 and 0.75 V for 3 depending on the axial ligands. Oxidation by electrolysis and/or radiolysis of 1, 2 and 4 gave their cationic radicals. The ESR spectra of 1(+.), 2(+.) and 4(+.) at 77 K were pseudo-axially symmetric with g tensors of g(perpendicular to) = 2.15 and g(parallel to) = 1.96, 2.18 and 1.95, and 2.20 and 1.96, respectively. Their hyperfine coupling indicates that their odd electron is delocalized equivalently onto the two axial phosphorous or arsenic atoms. The odd electron densities were estimated from the hyperfine coupling tensors as rho approximate to 0.1 on the P atoms of 1(+.) and 2(+.) and rho approximate to 0.15 on the As atoms of 4(+.). These results indicate that their singly occupied molecular orbital (SOMO) is the sigma (IrIr) orbital with sigma (IrP)* or sigma (IrAs)* character. DFT calculations for model complexes, [Ir-2(mu -O2CH)(2)Cl-2(CO)(2)(PH3)(2)](+.) (6(+.)) and [Ir-2(A-O2CH)(2)Cl-2(CO)(2)(AsH3)(2)](+.) (7(+.)), gave electronic structures consistent with the ESR results. (C) 2001 Elsevier Science B.V. All rights reserved.
• Ligand substitution reactions of bis(μ-acetato)dichlorodicarbonyldiiridium(II)
  作者：Masahiro Ebihara、Naohiro Kanematsu、Toshiharu Sakuma、Shinya Noritake、Takashi Kawamura

  DOI：10.1016/j.ica.2005.01.013

  日期：2005.4

  Seven diiridium(II) complexes were synthesized by ligand substitution reactions of [Ir-2(mu-O2CMe)(2)Cl-2(CO)(2)] (1) and [Ir-2(mu-O2CMe)(2)Cl-2(CO)(2)(PY)(2)] (2). The reaction of 2 with the silver salt of a less coordinating anion, AgSbF6, gave a cationic complex [Ir-2(mu-O2CMe)(2)Cl(CO)(2)(py)(3)]SbF6 (3). A tricarbonyl cationic complex [Ir-2(mu-O2CMe)(2)(CO)(3)Cl(py)(2)]SbF6 (4) was obtained under a CO atmosphere. Complex 2 reacted with AgO2CCF3 to give [Ir-2(mu-O2CMe)(2)Cl(O2CCF3)(CO)(2)(py)(2)] (5) in toluene. [Ir-2(mu-hiq)(2)(CO)(2)Cl-2] (Hhiq = 1-hydroxyisoquinoline, 6) was synthesized by the bridging-ligand substitution of I with Hhiq. Its axial adducts [Ir-2(mu-hiq)(2)Cl-2(CO)(2)L-2] (L = Mepy (4-methylpyridine), 7 or PPh3, 8) were synthesized by addition of the ligands to a suspension of 6. In the structures of 7 and 8, two iridium atoms are bridged by two hiq ligands in a head-to-tail arrangement. The reaction of I with Hmhp (2-hydroxy-4-methylpyridine) led to triply bridged [Ir-2(mu-mhP)(3)(CO)(2)Cl(Hmhp)] (9). In complex 9, all the mhp ligands bridge between the Ir atoms in a head-to-head manner. The Ir-Ir distances of 3, 4, 5, 7 and 8 are 2.6047(7), 2.6216(9), 2.5899(9), 2.5933(5) and 2.634(2) A, respectively, which are similar to those observed in [Ir-2(mu-O2CMe)(2)Cl-2(CO)(2)L-2]. The Ir-Ir distance of 2.5512(4) angstrom in 9 is shorter than in the other complexes. (c) 2005 Elsevier B.V. All rights reserved.