bis(heptamethylindenyl)cobalt(III) hexafluorophosphate | 137259-37-1

• 英文名称: bis(heptamethylindenyl)cobalt(III) hexafluorophosphate
• CAS: 137259-37-1
• 化学式: C₃₂H₄₂Co*F₆P
• 分子量: 630.643
• InChiKey: BQMWCEGWCJNELB-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  bis(heptamethylindenyl)cobalt(III) hexafluorophosphate 在 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 以43%的产率得到bis(heptamethylindenyl)cobalt(II)
  参考文献：
  名称：

  Synthesis and electronic structure of permethylindenyl complexes of iron and cobalt

  摘要：

  Fe(eta(5)-C9Me7)2 and Co(eta(5)-C9Me7)2 have been prepared by treatment of either FeCl2.xTHF (x congruent-to 2) or Co(acac)2 with LiInd* (Ind* = eta(5)-C9Me7) in THF. The cyclic voltammograms of both Fe(eta(5)-C9Me7)2 and Co(eta(5)-C9Me7)2 indicate that they are redox active with one-electron oxidations at E1/2 = -0.32 and -1.05 V vs SCE, respectively; both complexes exhibit second oxidations at E1/2 = 1.28 and 1.21 V vs SCE, respectively. The 17-electron and 18-electron cations [Fe(eta(5)-C9Me7)2]+PF6- and [Co(eta(5)-C9Me7)2]+PF6- were isolated by treatment of the neutral complexes with either [Fe(eta(5)-C5H5)2]+PF6- (for Fe) or NH4PF6 (for Co). Gas-phase UV photoelectron spectroscopy experiments on both Fe(eta(5)-C9Me7)2 and Co(eta(5)-C9Me7)2 show that the permethylindenyl ligand gives rise to lower first ionization energy (correlating with a more negative E1/2 value) than the Cp* (Cp* = eta(5)-C5Me5) ligand for Fe, while in the Co analogue the reverse is found. EPR and magnetic susceptibility experiments on [Fe(eta(5)-C9Me7)2]+PF6- and Co(eta(5)-C9Me7)2 both in solution and the solid state yield magnetic moments of 2.09-mu(B) for {Fe(eta(5)-C9Me7)2}+PF6- and 1.59-mu(B) for Co(eta(5)-C9Me7)2.

  DOI：

  10.1021/om00037a016
• 作为产物：
  描述：

  lithium heptamethylindenide 、 cobalt acetylacetonate 在 NH₄PF₆ 作用下， 以 四氢呋喃 为溶剂， 以47%的产率得到bis(heptamethylindenyl)cobalt(III) hexafluorophosphate
  参考文献：
  名称：

  Synthesis and electronic structure of permethylindenyl complexes of iron and cobalt

  摘要：

  Fe(eta(5)-C9Me7)2 and Co(eta(5)-C9Me7)2 have been prepared by treatment of either FeCl2.xTHF (x congruent-to 2) or Co(acac)2 with LiInd* (Ind* = eta(5)-C9Me7) in THF. The cyclic voltammograms of both Fe(eta(5)-C9Me7)2 and Co(eta(5)-C9Me7)2 indicate that they are redox active with one-electron oxidations at E1/2 = -0.32 and -1.05 V vs SCE, respectively; both complexes exhibit second oxidations at E1/2 = 1.28 and 1.21 V vs SCE, respectively. The 17-electron and 18-electron cations [Fe(eta(5)-C9Me7)2]+PF6- and [Co(eta(5)-C9Me7)2]+PF6- were isolated by treatment of the neutral complexes with either [Fe(eta(5)-C5H5)2]+PF6- (for Fe) or NH4PF6 (for Co). Gas-phase UV photoelectron spectroscopy experiments on both Fe(eta(5)-C9Me7)2 and Co(eta(5)-C9Me7)2 show that the permethylindenyl ligand gives rise to lower first ionization energy (correlating with a more negative E1/2 value) than the Cp* (Cp* = eta(5)-C5Me5) ligand for Fe, while in the Co analogue the reverse is found. EPR and magnetic susceptibility experiments on [Fe(eta(5)-C9Me7)2]+PF6- and Co(eta(5)-C9Me7)2 both in solution and the solid state yield magnetic moments of 2.09-mu(B) for {Fe(eta(5)-C9Me7)2}+PF6- and 1.59-mu(B) for Co(eta(5)-C9Me7)2.

  DOI：

  10.1021/om00037a016

文献信息

• Synthesis and characterisation of permethylindenyl complexes of cobalt and chromium: crystal structures of [Cr(η⁵-C₉Me₇)₂], [Co(η⁵-C₉Me₇)₂][PF₆] and [Cr(η⁵-C₉Me₇)₂][PF₆]
  作者：Dermot O'Hare、Vince J. Murphy、Nikolas Kaltsoyannis

  DOI：10.1039/dt9930000383

  日期：——

  Treatment of lithium heptamethylindenide with either anhydrous [Co(acac)2] (acac = acetylacetonate) or CrCl2 in tetrahydrofuran (thf) gave [Co(eta5-C9Me7)2] and [Cr(eta5-C9Me7)2] respectively. Single-crystal X-ray studies showed that [Cr(eta5-C9Me7)2] belongs to the centrosymmetric space group Pbca with a = 19.333(10), b = 14.586(9), c = 9.241 (2) angstrom, Z = 4, R = 0.043 and R' = 0.047. The metal centre lies on a crystallographic inversion centre and the permethylindenyl rings adopt a staggered conformation with a M-C9Me7 (C5-centroid) distance of 1.81 (2) angstrom. Gas-phase UV photoelectron spectroscopy experiments on [Cr(eta5-C9Me7)2] yield a first ionisation potential of 4.67 eV. The complexes [Co(eta5-C9Me7)2] [PF6] and [Cr(eta5-C9Me7)2] [PF6] were isolated by treatment of the neutral complexes with NH4PF6 in thf. Single-crystal X-ray studies show that both of these complexes belong to the centrosymmetric space group P1BAR. For [Co(eta5-C9Me7)2] [PF6], a = 14.332(15), b = 16.661 (11), c = 1 4.426 (15) angstrom, alpha = 109.55 (10), beta = 89.99 (10), gamma = 112.75(9), Z = 2, R = 0.064 and R' = 0.071, average M-C9Me7 (C5-centroid) distance = 1.68(2) angstrom. For [Cr(eta5-C9Me7)2] [PF6], a = 14.297(8), b = 16.842(9), c = 14.169(9) angstrom, alpha = 109.10(5), beta = 90.06(5), gamma = 111.49(4)degrees, Z = 2, R = 0.075, R' = 0.095, average M-C9Me7 (C5-centroid) distance = 1.84(1) angstrom. The cyclic voltammogram of [Cr(eta5-C9Me7)2][PF6] in MeCN indicates that this complex is redox active with a one-electron reduction at E1/2 = -1.15 V vs. saturated calomel electrode (SCE). The solid-state magnetic susceptibility data for [Co(eta5-C9Me7)2], [Cr(eta5-C9Me7)2] and [Cr(eta5-C9Me7)2] [PF6] can be modelled by the Curie law (chi(M) = C/T) in the temperature range 4-300 K with mu(eff) = 1.65, 2.67 and 3.47 for the three complexes respectively. The latter exhibits an axially symmetric EPR signal at 6 K with g(parallel-to) = 1.99 (m(s) = -3/2 --> m(s) = -1/2) and the double quantum transition g(perpendicular-to) = 4.33 (m(s) = -3/2 --> m(s) = 1/2), [Cr(eta5-C9Me7)2] also exhibits an axially symmetric powder line-shape at 11 K with g(parallel-to) = 2.04 and g(perpendicular-to) = 2.06.