[Pd(η5-C5H5)Fe(η5-C5H3CH=NCH2Ph)(μ-Cl)2] | 144496-08-2

• 英文名称: [Pd(η5-C5H5)Fe(η5-C5H3CH=NCH2Ph)(μ-Cl)2]
• 英文别名: [Pd(((η5-C5H3CH=NCH2Ph))Fe(η5-C5H5))(μ-Cl)]2
• CAS: 144496-08-2
• 化学式: C₃₆H₃₂Cl₂Fe₂N₂Pd₂
• 分子量: 888.103
• InChiKey: KECOSSRECFLTAA-ADLUWWIASA-L

反应信息

• 作为反应物：
  描述：

  3-己炔 、 [Pd(η5-C5H5)Fe(η5-C5H3CH=NCH2Ph)(μ-Cl)2] 以 氯仿 为溶剂， 以72%的产率得到[Pd(((EtC=CEt)2(η5-C5H3CH=NCH2Ph))Fe(η5-C5H5))Cl]
  参考文献：
  名称：

  Alkyne insertions into the σ-Pd–C(sp², ferrocene) bond of cyclopalladated complexes containing Schiff bases derived from ferrocene. Crystal structures of [Pd{[(EtCCEt)₂(η⁵-C₅H₃CRNCH₂Ph)]Fe(η⁵-C₅H₅)}Cl](R = H or Me)

  摘要：

  Reactions of di-mu-chloro-bridged cyclopalladated compounds [{Pd[(eta(5)-C(5)H(3)CR = NR')Fe(eta(5)-C5H5)](mu-Cl)}(2)] (R = H, Ph or Me, R' = CH(2)Ph; R = H, R' = CH(2)CH(2)Ph) with alkynes R '' C = CR '' (R '' = Et or Ph) have been studied. In all cases these reactions produce nine-membered metallocycles [Pd{[(R '' C = CR '')(2)(eta(5)-C(5)H(3)CR = N R')]Fe(eta(5)-C5H5)}Cl] (R '' = Et or Ph), which arise from a double insertion of the alkyne. Compounds [Pd{[(EtC = CEt)(2)(eta(5)-C(5)H(3)CR = NCH(2)Ph)]Fe(eta(5)-C5H5)}Cl] (R = H 4a or Me 4d) have been characterized structurally. Complex 4a is monoclinic, space group C2/c, with a = 30.783(4). b = 11.320(2), c =20.181(3) Angstrom and beta = 127.23(3)degrees; compound 4d is also monoclinic space group P2/a, with a = 20.308(4), b =11.075(2), c =12.565(2) Angstrom and beta = 92.01(3)degrees. These structural studies confirm the existence of a bicyclic system arising from the fusion of a nine-membered ring and the C5H3 moiety of the ferrocenyl moiety. The differences observed in the reactivity of the sigma(Pd-C-sp2,C- ferrocene) bond in the cyclopalladated compounds [{Pd[eta(5)C(5)H(3)CRFe(eta(5)-C5H5)](mu-Cl)}(2)] (R = H, Ph or Me) and in [{Pd[(eta(5)-C(5)H(3)CH(2)NMe(2))Fe(eta(5)-C5H5)](mu-Cl)}(2)] can be explained in terms of the electron donor ability of the chelated ligand. This. property is reflected mainly in the redox potential of the iron centre.

  DOI：

  10.1039/dt9950001839

文献信息

• 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
  作者：Concepción López、Ramón Bosque、Xavier Solans、Mercè Font-Bardía、David Tramuns、George Fern、Jack Silver

  DOI：10.1039/dt9940003039

  日期：——

  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.