Re3(μ-H)3(CO)10(pyridine)2 | 87526-43-0

• 英文名称: Re3(μ-H)3(CO)10(pyridine)2
• 英文别名: Re3(μ-H)3(CO)10(Py)2
• CAS: 87526-43-0
• 化学式: C₂₀H₁₃N₂O₁₀Re₃
• 分子量: 999.952
• InChiKey: OUOCTYRISHNMFM-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  Re3(μ-H)3(CO)10(NCMe)2 在 pyridine 作用下， 以 not given 为溶剂， 生成 Re3(μ-H)3(CO)10(pyridine)2
  参考文献：
  名称：

  通过氧化[re 3（μ-H）4（CO）10 ] -获得的反应性和多功能的tri羰基簇。re 3（μ-H）3（CO）10（NCMe）2的合成，x射线表征和反应性

  摘要：

  CF 3 SO 3 H在乙腈中氧化[Re 3（μ-H）4（CO）10 ] -，得到新的络合物Re 3（μ-H）3（CO）10（NCMe）2。它包含一个金属原子的三角形，其边缘由氢化物桥接（平均ReRe3.266Å）。以跨双轴方式与两种金属键合的乙腈配体很容易被取代，得到各种衍生物。

  DOI：

  10.1016/0022-328x(83)80144-2

文献信息

• Protonation reactions of the triangular cluster anion [Re3(μ-H)3(μ-NC5H4)(CO)10]− containing an orthometalated pyridine molecule
  作者：Tiziana Beringhelli、Giuseppe D'Alfonso、Monica Panigati

  DOI：10.1016/s0022-328x(96)06703-4

  日期：1997.1

  The [Re-3(mu-H)(3)(mu-NC5H4)(CO)(10)](-) triangular cluster anion 2 containing a bridging orthometalated pyridine moiety reacts with strong acids, in the presence of acetonitrile, to give the cisoid and transoid diaxial isomers of [Re-3(mu-H)(3)(CO)(10)(NCMe)(Py)] (4a and 4b) containing a terminally bound pyridine. The major isomer 4a, identified as the transoid species, is thermodynamically favoured in solvents of low polarity (4a/4b equilibrium ratio, at 295 K, 1.9 in MeCN, 2.5 in Me(2)CO, 4.9 in CH2Cl2). The rate of interconversion of the isomers varies with the solvent, ruling out an intramolecular process. Experiments with deuterated isotopomers of 2 have shown that the added proton is distributed among two of the three hydridic sites and the ortho-position of the terminally bound pyridine. The protonation has also been performed in the absence of added ligands, with acids with weakly coordinating anions (CF3SO3H or HBF4/Et(2)O): the NMR data suggest the formation of derivatives analogous to the isomers 4, in which the nitrile ligand is replaced by very poor donors, such as CF3SO3-, BF4- or Et(2)O. Successive substitution reactions indicate the following thermodynamic scale of nucleophilicity towards the vacant site of the Re-3(mu-H)(3)(CO)(10)(Py) fragment: BF4-, Et(2)O, H2O [ CF3SO3- [ Me(2)CO much less than MeCN [ Cl-, Py. Under CO atmosphere, both the isomers 4 give the novel neutral complex [Re-3(mu-H)(3)(CO)(11)(Py)] (k(obs)(I) = 4.21(2) x 10(-5)s(-1), at 300 K, in CO saturated acetone solution), which has been also obtained by protonation of the previously known [Re-3(mu-H)(2)(CO)(11)(Py)](-) anion. The reaction of 4 with pyridine is much faster than with CO, and in a few minutes both the isomers give the previously known trans-diaxial [Re-3(mu-H)(3)(CO)(10)(Py)(2)] (7a) complex. The same complex is obtained by reacting trans-diaxial [Re-3(mu-H)(3)(CO)(10)(NCMe)(2)] with pyridine, the monosubstitution derivatives 4 being present only as intermediates, with a low steady state concentration. A kinetic cis/trans ratio higher than the thermodynamic one has been found both for 4 and 7, in all the reactions studied.
• Reactions of the unsaturated anions [H3Re3(CO)10]2− and [H4Re3(CO)10]− with iodine in various solvents. X-ray characterization of the derivative H3Re3(CO)10(py)2
  作者：G. Ciani、G. D'Alfonso、M. Freni、P. Romiti、A. Sironi

  DOI：10.1016/s0022-328x(00)82416-x

  日期：1980.3