[Pd(N-phenylbenzaldimine(-1H))(μ-succinimidato)]2 | 104710-89-6

• 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: [Pd(N-phenylbenzaldimine(-1H))(μ-succinimidato)]2
• 英文别名: [Pd(Phbz)(μ-succ)]2
• CAS: 104710-89-6
• 化学式: C₃₄H₂₈N₄O₄Pd₂
• 分子量: 769.461
• InChiKey: HCLVSIOABWAQLN-YXWSOBMZSA-L

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

• 作为反应物：
  描述：

  [Pd(N-phenylbenzaldimine(-1H))(μ-succinimidato)]2 、 三苯基膦 以 二氯甲烷 为溶剂， 以76%的产率得到[Pd(N-phenylbenzaldimine(-1H))(succinimidato)(PPh₃)]
  参考文献：
  名称：

  Synthesis and Characterization of Imine-Palladacycles Containing Imidate “Pseudohalide” Ligands: Efficient Suzuki–Miyaura Cross-Coupling Precatalysts and Their Activation To Give Pd⁰L_n Species (L = Phosphine)

  摘要：

  Dinuclear palladacyclic complexes [{Pd(C boolean AND N)-(mu-NCO)}(2)] (C boolean AND N = N-phenylbenzaldimine, Phbz) containing asymmetric imidato units (-NCO = succinimidate (succ; 1), phthalimidate (phthal; 2), maleimidate (mal; 3), 2,3-dibromomaleimidate (2,3-diBrmal; 4), glutarimidate (glut; 5)) have been readily prepared by reaction between the di-mu-acetate precursor and cyclic imide ligands in a 1:2 molar ratio. Base treatment of the less acidic ligands 2-oxazolidone and delta-valerolactame with KOH/MeOH was required to give analogous -NCO- bridged complexes (6 and 7). Reactions of the dinuclear complexes with tertiary phosphines provide novel mononuclear N-bonded imidate derivatives of the general formula [Pd(Phbz)-(imidate)(PR3)] (R = Ph (a), 4-F-C6H4 (b), 4-MeO-C6H4 (c), CH2CH2CN (d)). The application of these novel palladacyclic complexes as precatalysts for the Suzuki-Miyaura cross-coupling reactions of both aryl and benzyl bromides with phenylboronic acid has been examined. The acetate adducts [Pd(Phbz)(CH3COO)(PR3)] (8a,c) were prepared to assess the role of imidate ligands in catalyst performance. The mononuclear imidate derivatives possess greater activity than the parent dinuclear complexes, exhibiting comparable performance in the cross-coupling of benzyl bromide with arylboronic acids to the best examples reported in the literature. The mononuclear imidate derivatives give a common (PdLn)-L-0 intermediate, as inferred by the release of the organic fragment (first reductive elimination product). Catalyst activation occurs by reaction of phenylboronic acid with the palladacyde in the absence of exogenous base (as shown by GC-MS and ESI-MS), with implications for the reliable comparison of catalyst performance across a series of related precatalysts (e.g., how catalyst/reagents are mixed and what is their order of addition). The single-crystal X-ray structures of compounds 4, 7, 1d, 3c, and 8a have been determined.

  DOI：

  10.1021/om2002443
• 作为产物：
  描述：

  丁二酰亚胺 、 [{Pd(N-benzylideneaniline)(μ-acetate)}₂] 以 丙酮 为溶剂， 以80%的产率得到[Pd(N-phenylbenzaldimine(-1H))(μ-succinimidato)]2
  参考文献：
  名称：

  Synthesis and Characterization of Imine-Palladacycles Containing Imidate “Pseudohalide” Ligands: Efficient Suzuki–Miyaura Cross-Coupling Precatalysts and Their Activation To Give Pd⁰L_n Species (L = Phosphine)

  摘要：

  Dinuclear palladacyclic complexes [{Pd(C boolean AND N)-(mu-NCO)}(2)] (C boolean AND N = N-phenylbenzaldimine, Phbz) containing asymmetric imidato units (-NCO = succinimidate (succ; 1), phthalimidate (phthal; 2), maleimidate (mal; 3), 2,3-dibromomaleimidate (2,3-diBrmal; 4), glutarimidate (glut; 5)) have been readily prepared by reaction between the di-mu-acetate precursor and cyclic imide ligands in a 1:2 molar ratio. Base treatment of the less acidic ligands 2-oxazolidone and delta-valerolactame with KOH/MeOH was required to give analogous -NCO- bridged complexes (6 and 7). Reactions of the dinuclear complexes with tertiary phosphines provide novel mononuclear N-bonded imidate derivatives of the general formula [Pd(Phbz)-(imidate)(PR3)] (R = Ph (a), 4-F-C6H4 (b), 4-MeO-C6H4 (c), CH2CH2CN (d)). The application of these novel palladacyclic complexes as precatalysts for the Suzuki-Miyaura cross-coupling reactions of both aryl and benzyl bromides with phenylboronic acid has been examined. The acetate adducts [Pd(Phbz)(CH3COO)(PR3)] (8a,c) were prepared to assess the role of imidate ligands in catalyst performance. The mononuclear imidate derivatives possess greater activity than the parent dinuclear complexes, exhibiting comparable performance in the cross-coupling of benzyl bromide with arylboronic acids to the best examples reported in the literature. The mononuclear imidate derivatives give a common (PdLn)-L-0 intermediate, as inferred by the release of the organic fragment (first reductive elimination product). Catalyst activation occurs by reaction of phenylboronic acid with the palladacyde in the absence of exogenous base (as shown by GC-MS and ESI-MS), with implications for the reliable comparison of catalyst performance across a series of related precatalysts (e.g., how catalyst/reagents are mixed and what is their order of addition). The single-crystal X-ray structures of compounds 4, 7, 1d, 3c, and 8a have been determined.

  DOI：

  10.1021/om2002443