Os3(CO)10(η(2)-pyridine-2-carbaldehyde N-propylimine) | 221192-60-5

• 英文名称: Os3(CO)10(η(2)-pyridine-2-carbaldehyde N-propylimine)
• CAS: 221192-60-5
• 化学式: C₁₉H₁₂N₂O₁₀Os₃
• 分子量: 998.912
• InChiKey: BKKYGXCGNYAQNW-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  Os3(CO)10(pyridine-2-carbaldehyde N-propylimine) 以 甲苯 为溶剂， 生成 Os3(CO)10(η(2)-pyridine-2-carbaldehyde N-propylimine)
  参考文献：
  名称：

  Mechanistic study of the photoisomerization of Os3(CO)10(L) in which L (L=1,4-di-R-1,4-diazabutadiene (R-DAB) or pyridine-2-carbaldehyde N-R-imine (R-PyCa)) changes its coordination from σ, σ-N,N′ into σ-N, μ2-N′, η2-CN′

  摘要：

  The triangular clusters Os-3(CO)(10)(alpha-diimine) photoisomerize to give the imine-bridged clusters Os-3(CO)(10)(sigma-N, mu(2)-N', eta(2)-C=N'-alpha-diimine) if the alpha-diimine has a reactive imine bond as in the case of R-DAB (1,4-di-R-1,4-diazabutadiene) or R-PyCa (pyridine-2-carbaldehyde N-R-imine). The products are identified by comparing their spectroscopic (IR, UV-vis,H-1-NMR) data with those of compounds reported in the literature. The quantum yield of the photoreaction decreases with an increase of the steric bulk of the alpha-diimine. Upon irradiation at low temperature the clusters produce unstable species? which transform into the final products on raising the temperature. The R-PyCa clusters produce a single intermediate, the R-DAB clusters three different ones. Some intermediates are assigned by comparing their IR and W-vis spectra with those of known species. A reaction mechanism is proposed for the photoisomerization, in which visible excitation causes the homolytic cleavage of an Os-Os bond with formation of a biradical. This biradical undergoes an intramolecular radical coupling reaction of the Os+(CO)(2)(alpha-diimine(.-)) and Os-.(CO)(4) radical sites with formation of an imine-bridged species, which is unstable because of a mismatch between the coordination of the two Os atoms. This mismatch is lifted by transfer of a CO ligand from one Os to the other via two CO-bridged (Os-CO-N) intermediates, which are detected at low temperature. This mechanism depicts a route along which the CO ligands of a cluster may move to compensate for an unbalance in metal-coordination. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)00955-3