[Ir2(μ-O2CMe)2Cl2(CO)2(PCy3)2]*CH2Cl2 | 392233-20-4

• 英文名称: [Ir2(μ-O2CMe)2Cl2(CO)2(PCy3)2]*CH2Cl2
• CAS: 392233-20-4
• 化学式: CH₂Cl₂*C₄₂H₇₂Cl₂Ir₂O₆P₂
• 分子量: 1275.26
• InChiKey: UGRDBXGEEKIKCK-UHFFFAOYSA-J

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：
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反应信息

• 作为产物：
  描述：

  二氯甲烷 、 bis(μ-acetato)dicarbonyldichlorodiiridium(II) 、 三环己基膦 以 甲苯 为溶剂， 以19%的产率得到[Ir2(μ-O2CMe)2Cl2(CO)2(PCy3)2]*CH2Cl2
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1016/s0020-1693(01)00615-6