Os3(CO)10(2,2'-bipyridine) | 172098-21-4

• 英文名称: Os3(CO)10(2,2'-bipyridine)
• 英文别名: decacarbonyl(2,2'-bipyridine)triosmium
• CAS: 172098-21-4；202661-33-4
• 化学式: C₂₀H₈N₂O₁₀Os₃
• 分子量: 1006.89
• InChiKey: HOHRTSPUYRYRAZ-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：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  吡啶 、 Os3(CO)10(2,2'-bipyridine) 以 吡啶 为溶剂， 生成 (-)Os(CO)4-Os(CO)4-Os(+)(pyridine)(CO)2(2,2'-bipyridine)
  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：

  2,2'-联吡啶 、 十二羰基三锇 以 二氯甲烷 、 乙腈 为溶剂， 以60%的产率得到Os3(CO)10(2,2'-bipyridine)
  参考文献：
  名称：

  Photochemistry of [Ru3(CO)12] with nitrogen heterocycles

  摘要：

  研究了[M 3 (CO) 12 ]（M = Ru 1a 或 Os 1b）与氮杂环的光化学作用。在所有情况下，光解都会导致光置换产物，杂环会抑制光破碎途径。1a 与吡啶 (py) 形成正金属化复合物 [Ru 3 H(CO) 10 (C 5 H 4 N)] 2a。用锇可以分离出简单的取代产物[Os 3 (CO) 11 (py)]3b。用 2-甲基吡啶（mby）分别从 1a 和 1b 生成 [Ru 3 H(CO) 10 (2-MeC 5 H 3 N)] 5a 和 [Os 3 (CO) 11 (mpy)] 6b。在 2,6-二甲基吡啶中没有观察到净光反应。1a 和 1b 与 2,2′-联吡啶光解后生成 [M 3 (CO) 10 (bipy)]（M = Ru 7a 和 Os 7b）。通过单晶 X 射线衍射研究获得了 7b 的分子结构。1a 和 1b 与哒嗪（pydz）发生光解反应，生成取代产物 [M 3 (CO) 10 (pydz)]（M = Ru 8a 或 Os 8b）。

  DOI：

  10.1039/a702099f

文献信息

• Photochemistry of the Clusters Os3(CO)10(L) (L = 2,2'-Bipyridine, 2,2'-Bipyrimidine, 2,3-Dipyrid-2-ylpyrazine, 2,3-Dipyrid-2-ylbenzoquinoxaline). Reversible Opening of an Os-Os Bond with Formation of a Zwitterion
  作者：J. W. M. van Outersterp、M. T. Garriga Oostenbrink、H. A. Nieuwenhuis、D. J. Stufkens、F. Hartl

  DOI：10.1021/ic00129a016

  日期：1995.12

  The complexes Os-3(CO)(10)(L)(L = 2,2'bipyridine (bpy), 2,2'-bipyrimidine (bpym), 2,3-dipyrid-2-ylpyrazine (dpp), and 2,3-dipyrid-2-ylbenzoquinoxaline (dpb)) were synthesized, and their low-energy Os --> L (MLCT) transitions were characterized with resonance Raman spectroscopy. Continuous wave excitation into the MLCT transitions does not lead to product formation. However, rapid-scan TR and nano- and picosecond time-resolved absorption spectra show the formation of a transient species (for L = bpy, bpym, and dpp) which reacts back to give the parent complex. In toluene the transient has a lifetime of less than in nr and is assigned to an MLCT state of the cluster. In coordinating solvents a different transient species is observed with a lifetime that strongly depends on the coordinating ability of the solvent and the basic properties of L (200-900 ns in tetrahydrofuran (THF), 5-20 s in CH3CN). The transient species could even be obtained as a stable photoproduct by reaction in 2-MeTHF at 113 K and upon irradiation at room temperature in the presence of a halide salt, The transient species is proposed to be the zwitterion Os-(CO)(4)-Os(CO)(4)-Os+(CO)(2)(S)(L). The positive charge of the metal in the Os+(CO)(2)(S)(L) moiety is evident from the Raman and H-1-NMR spectral the coordination of the solvent from its large influence on the lifetime, and the absorption maximum of the transient intermediate, Since the zwitterion. is already formed within 50 ps after the laser pulse, it is most probably produced by reaction from the MLCT state(s). A coordinating solvent molecule may initiate this reaction by coordination to the metal center of the Os(CO)(2)(alpha-diimine) fragment in its MLCT state. The extra negative charge donated by the solvent may then cause a heterolytic splitting of an Os-Os bond with formation of thp zwitterion.