[7,10-μ-H-7-CO-7,7-(PPh3)2-isonido-7,8,9-ReC2B7H9] | 911109-46-1

• 英文名称: [7,10-μ-H-7-CO-7,7-(PPh3)2-isonido-7,8,9-ReC2B7H9]
• CAS: 911109-46-1
• 化学式: C₃₉H₄₀B₇OP₂Re
• 分子量: 848.578
• InChiKey: HOJVHSLDXJJIBL-MKHWIZBJSA-N

反应信息

• 作为产物：
  描述：

  [HNMe3][3,3-(CO)2-3,3-Cl2-closo-3,1,2-ReC2B9H11] 、 三苯基膦 以 四氢呋喃 为溶剂， 以18%的产率得到[7,10-μ-H-7-CO-7,7-(PPh3)2-isonido-7,8,9-ReC2B7H9]
  参考文献：
  名称：

  Dual Fluorescence from an Isonido Re^III Rhenacarborane Phosphine Complex, [7,10-μ-H-7-CO-7,7-(PPh₃)₂-isonido-7,8,9-ReC₂B₇H₉]

  摘要：

  The complex [7,10-beta-H-7-CO-7,7-(PPh3)(2)-isonido-7,8,9-ReC2B7H9]has been synthesized by treatment of the complex salt [NHMe3][3,3-Cl-2-3,3-(CO)(2)-closo-3,1,2-ReC2B9H11] with PPh3 in refluxing THF (tetrahydrofuran) and isolated as intensely colored orange-red microcrystals. Spectroscopic NMR and IR data have suggested that the product has a highly asymmetric structure with two inequivalent PPh3 ligands and a single CO ligand. Measurement of B-11 NMR spectra in particular have indicated seven distinct boron vertexes, although the resulting cage degradation by removal of two BH vertexes was confirmed only following X-ray crystallographic analysis, which revealed the pentadecahedral isonido-7,8,9-ReC2B7 architecture. The B-11 NMR resonances span an enormous chemical shift range (Delta delta = 113), and this appears to be a direct consequence of the deshielding of the boron vertex directly opposite the quadrilateral ReCCB aperture. The new complex has been shown by electrochemical measurements to undergo a reversible one-electron oxidation. Digitally simulated cyclic voltammograms support a proposed square scheme (E-1/2 = 0.58, 0.69 V vs ferrocene) involving a reversible isonido-closo transition of the metallacarborane cage. Most unusually for a metallacarborane complex, ambient temperature solutions in CH2Cl2 and DMF have been shown to be intensely turquoise-blue fluorescent (lambda(em) = 442 nm, Phi = 0.012). Fluorescence spectroscopy measurements in MeTHF (2-methyltetrahydrofuran) glass at 77 K have indicated that the likely cause of such a broad emission is dual fluorescence (lambda(em) = 404, 505 nm), with both emissions displaying vibronic structure. Following excited- state lifetime decay analysis, the emissive behavior has been accredited to metal- perturbed (IL)-I-1 states, with the lower energy emission arising from a slight geometric distortion of the initially excited complex.

  DOI：

  10.1021/ic061071n