| 138353-36-3

• CAS: 138353-36-3
• 化学式: C₁₈H₂₃Fe₂NO₆Si
• 分子量: 489.163
• InChiKey: ORKSBCHHXUFJNE-GFDUFWMPSA-N

反应信息

• 作为产物：
  描述：

  1-(三甲基硅基)丙炔 、 tert-butylferraazetine 以 二氯甲烷 为溶剂， 生成 、
  参考文献：
  名称：

  Synthesis of 2-ferrapyridine complexes and their use as precursors for substituted pyridinones and pyrroles

  摘要：

  The 2-ferra-3-azetine complexes Fe2(mu-CHCH = NR)(CO)6, which form from the reaction of Fe2(mu-CH2)(CO)8 with phosphinimines, have been found to react photochemically with a variety of alkynes (R1C = CR2) by inserting the alkyne into the four-membered metallacycle to give the 2-ferrapyridine complexes Fe2(mu-C(R1)C(R2)CHCH = NR)(CO)6. Two of the 2-ferrapyridine complexes have been crystallographically characterized and shown to consist of six-membered metallacycles having adjacent iron and nitrogen atoms with this metallacycle pi-coordinated to the second iron atom by three carbon atoms and an Fe-Fe bond. Terminal alkynes (R1 = Me, Ph, Bu(t), SiMe3) undergo the insertion regioselectively to give only the 2-ferrapyridine isomer with the substituted carbon adjacent to the iron atom. Unsymmetrical internal alkynes insert to give generally a mixture of isomers which is influenced by the steric and electronic nature of the alkyne substituents. The 2-ferrapyridine complex Fe2(mu-C(Ph)CHCHCH = NBu(t))(CO)6 was shown to undergo a ring contraction when heated at 160-degrees-C under CO (500 psi) to give the new 2-ferra-3-azetine complex Fe2{mu-C[CH = C(Ph)(H)]CH = NR}(CO)6, which has also been crystallographically characterized and has a vinyl substituent attached to the 3-carbon of the 2-ferra-3-azetine ring. When heated, the 2-ferrapyridine complexes released 2-pyridinones and pyrroles with the ratio of these products dependent upon the ring substituents and the conditions employed. For example, the 2-ferrapyridine complexes prepared from terminal alkynes gave 2-pyridinones as the major products. The reaction of 2-ferrapyridine complexes prepared from internal alkynes gave mixtures of 2-pyridinones and pyrroles. The presence of electron-donating substituents on the 2-ferrapyridine ring favored the formation of 2-pyridinones, as did the presence of halide ion and an atmosphere of CO in the thermolysis reactions.

  DOI：

  10.1021/om00038a067