[Pd((η5-C5H5)Fe[(η5-C5H3)CH2NMe2])(μ-Cl)]2 | 1210287-36-7

• 英文名称: [Pd((η5-C5H5)Fe[(η5-C5H3)CH2NMe2])(μ-Cl)]2
• CAS: 1210287-36-7
• 化学式: C₂₆H₃₂Cl₂Fe₂N₂Pd₂
• 分子量: 767.993
• InChiKey: TYVCCNRLBGAFAP-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• 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：

  [Pd((η5-C5H5)Fe[(η5-C5H3)CH2NMe2])(μ-Cl)]2 在 PPh₃ 作用下， 以 苯 为溶剂， 以69.2%的产率得到[Pd(η5-C5H5)Fe(η5-C5H3CH2NMe2)Cl(PPh3)2]
  参考文献：
  名称：

  Effects of the nature of the nitrogen donor atom (sp²versus sp³) upon the properties and chemistry of palladated complexes with σ(Pd–C_sp2, ferrocene) bonds

  摘要：

  The NMR and Mossbauer spectra and electrochemistry of the N-donor ferrocenyl ligands [Fe(eta(5)-C5H5){(eta 5- C5H4CH=NCH(2)Ph)}] and [Fe(eta(5)-C5H5)(eta(5)-C(5)H(4)CH(2)NMe(2))] as-well as their mononuclear derivatives with sigma(Pd-C-sp2, ferrocene) bonds [Pd{(eta(5)-C5H5)Fe(eta(5)-C5H3CH=NCH(2)Ph)}Cl(L)], [Pd{(eta(5)-C5H5)Fe(eta(5)-C(5)H(3)CH(2)NMe(2))}Cl(L)] [L = 1-methylimidazole (mim) or PPh(3)], and [Pd{(eta(5)-C5H5) Fe(eta(5)-C(5)H(3)CH(2)NMe(2))}Cl(PPh(3))(2)] have been studied. Comparison of the data allows an understanding of the influence of the nature of the N-donor atom of the ferrocenyl moiety (sp(2) versus sp(3)) upon the properties of these compounds. In particular, the differences observed in the quadrupole splitting parameters obtained from Mossbauer spectroscopy reveal not only that the palladium(II) acts as an electron-withdrawing group in all these cyclometallated derivatives. but also that most of the electron density is withdrawn from the imine CH=N moiety in the derivatives containing ferrocenyl Schiff bases as ligands. The crystal structures of [Pd{(eta(5)-C5H5) Fe(eta(5)-C5H5CH=NCH(2)Ph)}Cl(PPh(3))] and [Pd{(eta(5)-C5H5)Fe(eta(5)-C(5)H(2)CH(2)NMe(2))}Cl(mim)] have been determined.

  DOI：

  10.1039/dt9940003039
• 作为试剂：
  描述：

  降冰片烯 、 4-碘苯甲醚 在 甲酸 、 三乙胺 、 [Pd((η5-C5H5)Fe[(η5-C5H3)CH2NMe2])(μ-Cl)]2 作用下， 以 二甲基亚砜 为溶剂， 反应 2.08h， 以99%的产率得到exo-2-(p-methoxyphenyl)bicxyclo[2.2.1]heptane
  参考文献：
  名称：

  Norbornene hydroarylation catalyzed by ferrocene palladacycle complexes

  摘要：

  两个含有双齿（C,N）和三齿（C,N,N）配体的钯环的二茂铁衍生物成功用于诺霍烯的水芳基化反应催化。

  DOI：

  10.1007/s11172-012-0204-5

文献信息

• Chloride-Promoted Synthesis of Cis Bis-Chelated Palladium(II) Complexes from Ortho-Mercurated Tricarbonyl(η⁶-arene)chromium Complexes
  作者：Alexsandro Berger、Jean-Pierre Djukic、Michel Pfeffer、Jérôme Lacour、Laurent Vial、André de Cian、Nathalie Kyritsakas-Gruber

  DOI：10.1021/om030433l

  日期：2003.12.1

  (η6-arene)Cr(CO)3 complexes. The study of the mechanism of this transmetalation reaction reveals the key role of the excess of chloride salt, which is necessary for the isolation of persistent heteroleptic bis-chelated Pd(II) complexes. This method was further applied to the synthesis of highly enantioenriched (+) and (−) samples of the ortho-chloropalladated 2-[tricarbonyl(η6-phenyl)chromium]pyridine, whose

  由的转移金属化反应的均聚物和杂顺式合成的新方法双-螯合的Pd（II）物质的邻汞化2- [三羰基（η 6 -苯基）铬]吡啶与一系列双（μ氯报道了在大量过量的氯化物盐[NMe 4 ] Cl存在下的四环芳族化合物。这些（CO）3铬结合的双-螯合的Pd（II）物质可被设计用于制备对映体纯的手性平面环钯（η 6 -arene）的Cr（CO）3复合体。对这种金属转移反应机理的研究揭示了过量氯化物盐的关键作用，这对于分离持久性杂配体双螯合的Pd（II）络合物是必需的。此方法进一步应用于高度对映体富集（+）的合成和（ - ）邻chloropalladated 2-样品[三羰基（η 6 -苯基）铬]吡啶，其对映体纯度，用抗磁Λ和Δ的辅助评估用作手性位移1 H NMR试剂的TRISPHAT盐。从通过X射线衍射分析确定的相应的绝对结构获得两种对映体富集的复合物的绝对构型。报道了六个新的杂合双螯合钯（II）配合物的分子结构。
• Influence of the electronic effects of phosphine ligands upon the properties of cyclopalladated complexes containing a σ(Pd—Csp2, ferrocene)bond X-Ray crystal structures of [Pd{(η5-C5H5)Fe[(η5-C5H3)C(Me)ξN(C6H4-4-Me)]}Cl(PPh3)] and [Pd{(η5-C5H5)Fe[(η5-C5H3)CH2NMe2]}Cl(PPh3)]
  作者：Concepción López、Ramón Bosque、Xavier Solans、Mercè Font-Bardia

  DOI：10.1039/a801737i

  日期：——

  The synthesis, characterization and study of the properties of the cyclopalladated compounds [Pd(η5-C5H5)Fe[(η5-C5H3)C(Me)N(C6H4-4-Me)]}Cl(L)] and [Pd(η5-C5H5)Fe[(η5-C5H3)CH2NMe2]}Cl(L)] (L=PPh3, PPh2Et, PPhEt2 or PEt3) are reported. The comparison of the electrochemical and electronic properties of these compounds has allowed us to elucidate the influence of the phosphine and chelate ligands upon the environment of the FeII. As a first approach to clarify the factors affecting the properties of these complexes, molecular orbital (MO) calculations using the PM3(tm) semiempirical method were also undertaken. [Pd(η5-C5H5)Fe[(η5-C5H3)C(Me)N(C6H4-4-Me)]}Cl(PPh3)] (3a) and [Pd(η5-C5H5)Fe[(η5-C5H3)CH2NMe2]} Cl(PPh3)] (3b) have also been characterized structurally. Complex 3a is triclinic, space group P, with a=12.795(2), b=11.534(2) and c=11.267(2) Å and α=106.660(10)°, β=98.660(10)° and γ=94.500(10)°; compound 3b is monoclinic, space group P21/a, with a=13.650(3), b=19.678(4) and c=10.169(2) Å and α=γ=90.0° and β=94.69(2)°. In both cases the molecules contain a [5,5] bicyclic system formed by a five-membered palladacycle and the C5H3 ring of the ferrocenyl moiety.

  报道了环钯化合物的合成、表征及其性质研究，这些化合物包括[Pd(η5-C5H5)Fe[(η5-C5H3)C(Me)N(C6H4-4-Me)]}Cl(L)]和[Pd(η5- )Fe[(η5- )CH2NMe2]}Cl(L)]（L=PPh3，PPh2Et，PPhEt2或PEt3）。通过比较这些化合物的电化学和电子性质，我们阐明了膦和螯合配体对FeII环境的影响。为了初步澄清影响这些复杂性质的因素，我们还采用了PM3(tm)半经验方法进行了分子轨道（MO）计算。[Pd(η5- )Fe[(η5- )C(Me)N( -4-Me)]}Cl(PPh3)]（3a）和[Pd(η5- )Fe[(η5- )CH2NMe2]}Cl(PPh3)]（3b）的结构也被表征。复合物3a是三斜晶系，空间群为P，a=12.795(2)，b=11.534(2)和c=11.267(2) Å，α=106.660(10)°，β=98.660(10)°和γ=94.500(10)°；化合物3b是单斜晶系，空间群为P21/a，a=13.650(3)，b=19.678(4)和c=10.169(2) Å，α=γ=90.0°和β=94.69(2)°。在这两种情况下，分子都包含一个由五元环钯环和二茂铁部分的 环形成的双环[5,5]系统。
• Asymmetric induction during carbonylation of an optically active organopalladium. A novel and versatile route to enantiomeric glycerides.
  作者：L.L. Troitskaya、V.I. Sokolov

  DOI：10.1016/0022-328x(85)87383-6

  日期：1985.4

  carbonylation of optically active [η5-C5H5Feη5- CH5H3CH2NMe2PdCl]2 (1) in prochiral diols, the asymmetric induction of a newly developed chiral centre by a chiral plane has been performed. For 2-O-benzyl- glycerol, the extent of asymmetric induction, that means diastereoselectivity, was found to be about 36%. The protection of a free hydroxyl followed by hydrolysis of a ferrocenoyl derivative resulted in

  在光学活性[η的羰基化的过程中5 -C 5 H ^ 5 Feη 5 - CH5H3CH2NMe2PdCl] 2（1中前手性二醇），在已经执行通过手性平面新开发的手性中心的不对称诱导。对于2- O-苄基甘油，发现不对称诱导的程度，这意味着非对映选择性，为约36％。保护游离羟基，然后水解二茂铁酰基衍生物，得到对映体2- O-苄基-3- O-三苯甲基-sn-甘油（4）可以用作光学活性单，二和三取代甘油酯合成中的关键中间体。通过1-棕榈酰-sn-甘油的制备的详细描述说明了该方法。
• Hemichelation, a Way To Stabilize Electron-Unsaturated Complexes: The Case of T-Shaped Pd and Pt Metallacycles.
  作者：Christophe Werlé、Corinne Bailly、Lydia Karmazin-Brelot、Xavier-Frédéric Le Goff、Louis Ricard、Jean-Pierre Djukic

  DOI：10.1021/ja4076327

  日期：2013.11.27

  situ formed tricarbonyl(η(6)-2-methylindenyl)chromium anion with a series of Pd and Pt metallacycles afforded new air-stable and persistent synfacial heterobimetallic complexes in which the metallacycle binds the indenyl fragment via its metal in an η(1) fashion, leaving the fourth coordination site at the chelated metal virtually vacant. The structures of eight of these novel complexes are disclosed

  提出了一种合成稳定的中性T形14电子Pd和Pt配合物的合理方法。它利用了三羰基(η(6)-茚基)铬阴离子的两亲性，其主要特性是作为半螯合配体，即一种非常规的异双位配体，能够通过共价键螯合金属中心。和非共价键，从而保持其不饱和价壳。原位形成的三羰基（η(6)-2-甲基茚基）铬阴离子与一系列 Pd 和 Pt 金属环的反应提供了新的空气稳定和持久的异质双金属配合物，其中金属环通过其金属结合茚基片段η(1) 方式，使螯合金属处的第四配位位点几乎空置。公开了这些新型复合物中的八种结构，并通过基于密度泛函理论的一系列理论方法（NBO、EDA、ETS-NOCV、AIM、NCI 区域分析）研究了它们的键合特征。理论表明，这些不寻常的双金属共面 η(1)-茚基-Pd/Pt 复合物结构的形成是由 Cr(CO)3 部分在 Pd/Pt 中心的第四个空位配位位点的吸引力库仑闭塞热力学驱动的。