| 143470-81-9

• CAS: 143470-81-9
• 化学式: C₂₂H₄₄Fe₂P₄
• 分子量: 544.18
• InChiKey: WNUWHEFPUODYTB-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  {diiron(μ2-η10-fulvalene)(C6H6)2}{PF6} 、 三甲基膦 在 Na/Hg 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 以38%的产率得到
  参考文献：
  名称：

  Fulvalenyl Mono- and Diiron Complexes:  Photolytic and Electron-Transfer-Induced Substitution of the Benzene Ligands by Phosphines and CO in the Diiron Fulvalenyl Dibenzene Complexes [Fe₂Fv(C₆H₆)₂]^2+/0. Generation of the Average-Valence Species [Fe₂FvL₆]³⁺ (L = Phosphine)

  摘要：

  The bi-sandwich complex [Fe(2)Fv(C6H6)(2)](2+)(PF6-)(2) (1(2+); Fv = mu(2)-eta(5):eta(5)-fulvalenyl, unless noted otherwise) synthesized from biferrocene, was photolyzed with visible light in acetonitrile in the presence of 1,2-bis(diphenylphosphino)ethane (dppe) or bis(diphenylphosphino)methane (dppm) at -15 degrees C to give [Fe(2)Fv(dppe)(2)(NCMe)(2)](2+)(PF6-)(2) (2a(2+)) or [Fe(2)Fv(dppm)(2)(NCMe)(2)](2+)(PF6-)(2) (2b(2+)). The complexes 2a(2+) and 2b(2+) reacted in refluxing 1,2-dichloroethane with CO to give [Fe(2)Fv(dppe)(2)(CO)(2)](2+)(PF6-)(2) (3a(2+)) and [Fe(2)Fv(dppm)(2)(CO)(2)](2+)(PF6-)(2) (3b(2+)), and 2a(2+) reacted similarly with PMe3 to give [Fe(2)Fv(dppe)(2)(PMe3)](2+)(PF6-)(2) (4(2+)). The dir;educed 38-electron (38e) complex 1 reacted at -15 degrees C with 1 atm of CO to give [Fe-2(mu(2)-eta(4):eta(4)-Fv)(CO)(6)] (7) and with PMe3 to give [Fe(2)Fv(PMe3)(4)] (9). When Na+PF6- was present in stoichiometric amounts in THF, these reactions followed a different course and Na+PF6--induced electron transfer (disproportionation) by irreversibly dislocating ion pairs: the reaction of 1 with 1 atm of CO gave [Fe(eta(5)-Fv)(eta(6)-C6H6), Na+PF6-] (5), and that with PMe3 gave [Fe(2)Fv(PMe3)(6)](2+)(PF6-)(2) (8(2+)) and the known complex [Fe(PMe3)(4)] (10). The cyclic voltammograms (CV) of 2a(2+) and 2b(2+) contain irreversible oxidation and reduction waves, but the CVs of 3a(2+) and 3b(2+) showed two close reversible monoelectronic reduction waves (no oxidation wave). The CVs of the hexaphosphine complexes indicated partially or fully irreversible reduction waves, respectively, but two reversible waves at +0.71 and +0.95 V for 4(2+) and +0.70 and +1.08 V for 8(2+) (vs SCE, Pt, DMF, 0.1 M n-Bu4NBF4 -30 degrees C). The bielectronic reduction of 2a(2+) and the bielectronic oxidation of 4(2+) and 8(2+) using redox reagents led to decomposition, but the monoelectronic oxidation of 4(2+) and 8(2+) using (p-Br-C6H4)(3)N+SbCl6- in CH2Cl2 gave the stable mixed-valence trications 4(3+) and 8(3+), for which the Mossbauer spectra showed delocalized average valency on the Mossbauer time scale. These studies have opened the route to a variety of mono- and diiron fulvalenyl organometallic compounds, confirming the great importance of the presence of Na+PF6-. This salt can change reaction pathways and, in particular, induce electron-transfer reactions, underlining the extraordinary electronic flexibility of the fulvalenyl Ligand and its ability to transfer the electron flow between two metal centers.

  DOI：

  10.1021/om961060+