Os3(CO)10(σN,μ2-N`,η2-CN`-C5H4N-2-C(H)N(i-Pr)) | 121566-50-5

• 英文名称: Os3(CO)10(σN,μ2-N`,η2-CN`-C5H4N-2-C(H)N(i-Pr))
• CAS: 121566-50-5
• 化学式: C₁₉H₁₂N₂O₁₀Os₃
• 分子量: 998.912
• InChiKey: XCHLUYNMRHJOPP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
  None
• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Os3(CO)10(σN,μ2-N`,η2-CN`-C5H4N-2-C(H)N(i-Pr)) 以 further solvent(s) 为溶剂， 生成 Os2(CO)6(σN,μ2-N`,η2-C=N`-C5H4N-2-C(H)N(i-Pr))
  参考文献：
  名称：

  Os 3（CO）10（C 5 H 4 N-2-C（H）NR）的两种异构体的合成与表征以及向正金属化HOs 3（C 5 H 3 N-2-C（H）的转化NR）（CO）9。第三部分 HOs 3（C 5 H 3 N-2-C（H）Ni-Pr）（CO）9的X射线结构

  摘要：

  Os 3（CO）10（MeCN）2在室温下在MeCN或甲苯中与R-Pyca†反应，生成Os 3（CO）10（R-Pyca）的两种异构体，它们的R-Pyca配体键合不同到Os 3（CO）10单元。在所有情况下Os 3（CO）10（R-Pyca（4e））（异构体A; 4a：R = c-Pr，4b：R = i-Pr，4c：R = neo-Pent，4d：R = t -Bu），其中含有螯合的4e供体R-Pyca配体和三个OsS键，可以分离出来。在R = c-Pr和R = i-Pr的情况下Os 3（CO）10（R-Pyca（6e））（异构体B; 5a：R = c-Pr，5b：R = i-Pr），其中仅存在两个OsS键，并且R-Pyca配体作为6e供体配体键合桥接两个未键合的Os原子，可以作为次要产物分离出来。

  DOI：

  10.1016/s0020-1693(00)86014-4
• 作为产物：
  描述：

  Os3(CO)10(pyridine-2-carbaldehyde N-isopropylimine) 以 甲苯 为溶剂， 生成 Os3(CO)10(σN,μ2-N`,η2-CN`-C5H4N-2-C(H)N(i-Pr))
  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