η5-2,5-diphenylphosphacymantrene | 69718-32-7

• 英文名称: η5-2,5-diphenylphosphacymantrene
• 英文别名: 1-phospha-2,5-diphenylcymantrene；2,5-diphenylphosphacymantrene；[Mn(CO)3(η5-C4H2PPh2)]
• CAS: 69718-32-7
• 化学式: C₁₉H₁₂MnO₃P
• 分子量: 374.214
• InChiKey: HYPHMDUQBGHSDY-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：
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反应信息

• 作为反应物：
  描述：

  η5-2,5-diphenylphosphacymantrene 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 以 二氯甲烷 为溶剂， 以77%的产率得到
  参考文献：
  名称：

  Brunet, Lionel; Mercier, Francois; Ricard, Louis, Angewandte Chemie, 1994, vol. 106, p. 812 - 816

  摘要：

  DOI：

文献信息

• First optically active P-alkoxy derivative of palladated phosphacymantrene: synthesis, structure, and chiroptical properties
  作者：A. F. Smol’yakov、A. G. Ginzburg、V. V. Bashilov、F. M. Dolgushin、P. V. Petrovskii、K. K. Babievsky、V. I. Sokolov

  DOI：10.1007/s11172-013-0145-7

  日期：2013.4

  The solvopalladation reaction of 2,5-diphenylphosphacymantrene with Na2PdCl4, AcONa, and optically active carbinol (S)-(−)-2-methylbutanol was carried out. Optically active complex 3 was obtained and characterized by X-ray diffraction analysis and circular dichroism (CD), 13C and 31P NMR, IR, and UV spectra.

  进行了 2,5-二苯基磷杂萁烯与 Na2PdCl4、AcONa 和光学活性甲醇 (S)-(-)-2-甲基丁醇的溶剂钯化反应。获得了光学活性配合物3，并通过X射线衍射分析和圆二色性(CD)、13C和31P NMR、IR和UV光谱进行表征。
• Amine-promoted nucleophilic addition of tert-butyl hydroperoxide to 2,5-diphenylphosphacymantrene: oxygen-oxygen bond cleavage and novel rearrangement with RO group transfer from oxygen to phosphorus
  作者：V. I. Sokolov、A. F. Smol´yakov、A. G. Ginzburg

  DOI：10.1007/s11172-014-0779-0

  日期：2014.11

  The reaction of 2,5-diphenyl-1-phosphacymantrene (1) with hydroperoxide Me3COOH was carried out in MeCN-Et2NH. The attack of nucleophile Me3COO– to the phosphorus atom in compound 1 followed by the Arbuzov-type rearrangement PIII → PV afforded complex 2 with the η4-phosphoryl ligand characterized by X-ray diffraction analysis, IR spectroscopy, and 1H, 13C, and 31P spectroscopy.

  2,5-二苯基-1-磷酰芴醇 (1) 与氢过氧化物 Me3COOH 的反应在 MeCN-Et2NH 中进行。亲核试剂 Me3COO– 攻击化合物 1 中的磷原子，然后进行 Arbuzov 型重排 PIII → PV 提供了具有 η4-磷酰基配体的配合物 2，通过 X 射线衍射分析、红外光谱和 1H、13C 和 31P 表征光谱学。
• Alkoxypalladation of 2,5-diphenylphosphacymantrene with sodium tetrachloropalladate in the presence of sodium acetate
  作者：A. G. Ginzburg、V. V. Bashilov、F. M. Dolgushin、V. I. Sokolov

  DOI：10.1007/s11172-008-0274-6

  日期：2008.9

  discovered reaction can be named alkoxypallada tion of 2,5 diphenylphosphacymantrene. Apparently, this is a unique example of solvometalation reactions, which usually occur at two doubly bonded atoms.5 A peculiar feature of this reaction is that the Pd atom and the OMe group attack the same P atom. 1H and 31P NMR spectra were recorded on a Bruker Avance 300 instrument (300 (1H) and 121.44 MHz (31P)).

  我们发现 2,5 diphenylphosphacymantrene1 (1) 在 NaOAc（摩尔比 1 : 1 : 1）的存在下，在 MeOH 中在室温下与 Na2PdCl4 反应生成红色配合物 (2)，其中起始化合物的磷原子1 由钯配位（方案 1）。这从 31P NMR 信号（δ –30.10 (1) 和 89.5 (2)）的强（几乎 120 ppm）低场位移中可以明显看出。配合物 2 的 1H NMR 光谱显示，除了苯基质子和磷酸环戊二烯基环的位置 3 和 4 中的两个质子的信号之外，还有另一个信号，该信号在起始化合物 1 的光谱中不存在：δ 处的双峰由于 OMe 基团的质子与磷结合，耦合常数为 3.65 (3 H) 3J = 14.8 Hz。在配合物 2 的红外光谱中，保留了片段 Mn(CO)3 的频率 ν(CO) 特征：1965 cm-1 处的宽频带（简并 E 型振动）和 2020
• The reaction of 2,5-diphenylphosphacymantrene with solid KOH in the presence of crown ethers: Synthesis of the anionic η4-phosphoryl manganese complexes
  作者：Vasily V. Bashilov、Allan G. Ginzburg、Alexander F. Smol’yakov、Fedor M. Dolguschin、Pavel V. Petrovskii、Viatcheslav I. Sokolov

  DOI：10.1016/j.jorganchem.2009.09.013

  日期：2009.12

  2,5-Diphenylphosphacymantrene (1) reacts with solid KOH in the presence of crown ethers in C6H6 or CH2Cl2 at room temperature adding OH nucleophile to the phosphorus atom to afford anionic complexes [(CO)(3)Mn-eta(4)-2,5-Ph2H2C4P(=O)H] [K-Crown](+), where Crown = 18-crown-6 (2) or dicyclohexyl-18-crown-6 (3). Complexes 2 and 3 are characterized by H-1, P-31, C-13 NMR and IR-spectra. The structure of 2 is established by X-ray crystal structure data. (C) 2009 Elsevier B. V. All rights reserved.
• Change of the coordination type for the phospholyl ligand under nucleophilic attack of H2O on phosphorus atom in 2,5-diphenylphosphacymantrene promoted by aliphatic amines
  作者：Allan G. Ginzburg、Vasily V. Bashilov、Fedor M. Dolgushin、Alexander F. Smol’yakov、Pavel V. Petrovskii、Viatcheslav I. Sokolov

  DOI：10.1016/j.ica.2011.01.094

  日期：2011.5

  eta(5)-2,5-Diphenylphosphacymantrene (1) in benzene or CH2Cl2 solution does not react with amines. However, with amines NHEt2, NEt3, NEt(i-Pr)(2) in excess and in the presence of small amounts of water 1 reacts to form anionic complexes [(CO)(3)Mn(eta(4)-Ph2H2C4P(=O)H] A(+), where cation A = H2NEt2+ (2a), HNEt3+ (2b), HN(Et)(Pr-i)(2)(+) (2c). Probably, first an unstable intermediate with P-OH bond is formed as a result of the attack by the activated H2O molecule at the P atom. Afterwards, the rapid rearrangement occurs with migration of H from O to P which leads to the ligand 2,5-diphenyl-1-H-phosphol-1-oxide, Ph2H2C4P(=O)H. Salts 2a-c have been characterized by H-1, P-31, C-13 NMR- and IR-spectra and the structures of 2a and 2c established by single crystal X-ray diffraction analyses. The phosphoryl ligand in anions 2a and 2c has the "envelope" conformation and is eta(4)-coordinated with Mn(CO)(3). The phosphorus atom is not involved in the coordination with Mn because the Mn-P distances (2.7670(4) and 2.7732(8) angstrom) are greater than the sum of covalent radii of P and Mn. (C) 2011 Elsevier B.V. All rights reserved.