[Os3(CO)10(2-acetylpyridine-N-isopropylimine)] | 202661-37-8

• 英文名称: [Os3(CO)10(2-acetylpyridine-N-isopropylimine)]
• 英文别名: Os3(CO)10(2-acetylpyridine N-isopropylimine)；[Os(CO)10(i-Pr-AcPy)]
• CAS: 202661-37-8；202661-00-5
• 化学式: C₂₀H₁₄N₂O₁₀Os₃
• 分子量: 1012.94
• InChiKey: HXJHRLSKYVMJAB-GKIVNCLMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• 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：

  丁腈 、 [Os3(CO)10(2-acetylpyridine-N-isopropylimine)] 以 further solvent(s) 为溶剂， 生成 (-)Os(CO)4-Os(CO)4-Os(+)(butyronitrile)(CO)2(2-acetylpyridine N-isopropylimine)
  参考文献：
  名称：

  Photochemistry of the Triangular Clusters Os₃(CO)₁₀(α-diimine): Homolysis of an Os−Os Bond and Solvent-Dependent Formation of Biradicals and Zwitterions

  摘要：

  Several clusters Os-3(CO)(10)(alpha-diimine) (alpha-diimine = pyridine-2-carbaldehyde N-R-imine or 1,4-di-R-1,4-diazabutadiene) were synthesized and studied with respect to their spectroscopic and photochemical properties. According to the resonance Raman spectra the visible absorption band of these clusters belongs to electronic transitions having Os-to-a-diimine charge transfer (MLCT) character with a variable degree of pi-delocalization within the Os(alpha-diimine) moiety. Upon irradiation into these transitions zwitterions Os-(CO)(4)-Os(CO)(4)-Os+-(S)(CO)(2)(alpha-diimine) are formed in coordinating solvents (S) and biradicals *Os(CO)(4)-Os(CO)(4)-Os+(CO)(2)(alpha-diamine(.-)) in noncoordinating solvents and in THF at ambient temperature. The zwitterions live seconds in nitrile solvents and minutes in pyridine, and they largely regenerate the parent clusters. Quantum yields of zwitterion formation are wavelength independent and range from 10(-2) to 3 x 10(-2) with an activation energy varying from 440 to 720 cm(-1). For one of the clusters the quantum yield of zwitterion formation in pyridine was studied in dependence of applied pressure. The activation volume Delta V-double dagger = +7.0 +/- 0.5 cm(3) mol(-1) derived from these measurements indicates that the effect of bond cleavage is partially offset by coordination of the solvent. In apolar solvents biradicals are formed instead of zwitterions, which could be detected with nanosecond time-resolved absorption spectroscopy, while their adducts with nitrosodurene were observed with EPR spectroscopy. Their lifetimes vary from 5 ns to 1 mu s depending on the solvent and the alpha-diimine. The biradicals transform into zwitterions in the presence of a Lewis base. in addition, they produce with low efficiency an isomeric product in which the cr-diimine bridges between two Os atoms. The formation of very similar photoproducts (biradicals, cr-diimine-bridged isomeric products, charge-separated species) as in the case of binuclear metal-metal-bonded complexes such as (CO)(5)MnMn(CO)(3)(alpha-diimine) points to the occurrence of a primary photoprocess in which an Os-Os bond is broken homolytically. This reaction most likely occurs from a reactive (3) sigma pi* state after surface crossing from the unreactive but optically accessible MLCT states.

  DOI：

  10.1021/ic9707319
• 作为产物：
  描述：

  bis(acetonitrile)decacarbonyltriosmium 、 N-(1-(pyridin-2-yl)ethylidene)propan-2-amine 以 四氢呋喃 为溶剂， 生成 [Os3(CO)10(2-acetylpyridine-N-isopropylimine)]
  参考文献：
  名称：

  Photochemistry of the Triangular Clusters Os₃(CO)₁₀(α-diimine): Homolysis of an Os−Os Bond and Solvent-Dependent Formation of Biradicals and Zwitterions

  摘要：

  Several clusters Os-3(CO)(10)(alpha-diimine) (alpha-diimine = pyridine-2-carbaldehyde N-R-imine or 1,4-di-R-1,4-diazabutadiene) were synthesized and studied with respect to their spectroscopic and photochemical properties. According to the resonance Raman spectra the visible absorption band of these clusters belongs to electronic transitions having Os-to-a-diimine charge transfer (MLCT) character with a variable degree of pi-delocalization within the Os(alpha-diimine) moiety. Upon irradiation into these transitions zwitterions Os-(CO)(4)-Os(CO)(4)-Os+-(S)(CO)(2)(alpha-diimine) are formed in coordinating solvents (S) and biradicals *Os(CO)(4)-Os(CO)(4)-Os+(CO)(2)(alpha-diamine(.-)) in noncoordinating solvents and in THF at ambient temperature. The zwitterions live seconds in nitrile solvents and minutes in pyridine, and they largely regenerate the parent clusters. Quantum yields of zwitterion formation are wavelength independent and range from 10(-2) to 3 x 10(-2) with an activation energy varying from 440 to 720 cm(-1). For one of the clusters the quantum yield of zwitterion formation in pyridine was studied in dependence of applied pressure. The activation volume Delta V-double dagger = +7.0 +/- 0.5 cm(3) mol(-1) derived from these measurements indicates that the effect of bond cleavage is partially offset by coordination of the solvent. In apolar solvents biradicals are formed instead of zwitterions, which could be detected with nanosecond time-resolved absorption spectroscopy, while their adducts with nitrosodurene were observed with EPR spectroscopy. Their lifetimes vary from 5 ns to 1 mu s depending on the solvent and the alpha-diimine. The biradicals transform into zwitterions in the presence of a Lewis base. in addition, they produce with low efficiency an isomeric product in which the cr-diimine bridges between two Os atoms. The formation of very similar photoproducts (biradicals, cr-diimine-bridged isomeric products, charge-separated species) as in the case of binuclear metal-metal-bonded complexes such as (CO)(5)MnMn(CO)(3)(alpha-diimine) points to the occurrence of a primary photoprocess in which an Os-Os bond is broken homolytically. This reaction most likely occurs from a reactive (3) sigma pi* state after surface crossing from the unreactive but optically accessible MLCT states.

  DOI：

  10.1021/ic9707319

文献信息

• Heterosite Effects in Novel Heteronuclear Clusters [Os ₂ Ru(CO) ₁₁ (PPh ₃ )] and [Os ₂ Ru(CO) ₁₀ (2‐acetylpyridine‐ <i>N</i> ‐isopropylimine)]
  作者：Frank W. Vergeer、Martin Lutz、Anthony L. Spek、Maria J. Calhorda、Derk J. Stufkens、František Hartl

  DOI：10.1002/ejic.200401040

  日期：2005.6

  unsaturated +Ru(CO)2(iPr-AcPy·–/0) moiety to bind a Lewis base, the heteronuclear biradical and zwitterionic photoproducts live significantly shorter than their triosmium counterparts. The influence of the weaker Os2–Ru(iPr-AcPy) bond on the redox reactivity is clearly reflected in very reactive radical anions formed upon electrochemical reduction of [Os2Ru(CO)10(iPr-AcPy)]. The dimer [–Os(CO)4-Os(CO)4-Ru(CO)2(iPr-AcPy)]22–

  对混合金属簇 [Os2Ru(CO)12] 的新合成路线及其 PPh3 和 iPr-AcPy（iPr-AcPy = 2-乙酰吡啶-N-异丙基亚胺）衍生物的合成进行了描述。新型簇 [Os2Ru(CO)11(PPh3)] 和 [Os2Ru(CO)10(iPr-AcPy)] 的分子结构是基于 Os2Ru 和相应 Os3 物种的结晶固溶体确定的。结构表明，路易斯碱的配位仅发生在 [Os2Ru(CO)12] 的钌位点，这与对这些化合物的几种结构异构体的密度泛函理论 (DFT) 计算一致。根据时间相关的 DFT 结果，[Os2Ru(CO)10(iPr-AcPy)] 的最低光学可及激发态具有主要的 σ(Ru-Os2)π*(iPr-AcPy) 特征，部分 σ σ *（Ru-Os2）贡献。在弱配位 2-氯丁烷中，激发态的寿命 τ = 10.4 ± 1.2 ps，并且产生双自由基的速度比观察到的 [Os3(CO)10(iPr-AcPy)