Os3(CO)10(pyridine-2-carbaldehyde N-isopropylimine) | 121566-50-5

• 英文名称: Os3(CO)10(pyridine-2-carbaldehyde N-isopropylimine)
• CAS: 121566-50-5；221192-59-2；202661-36-7；121566-43-6
• 化学式: C₁₉H₁₂N₂O₁₀Os₃
• 分子量: 998.912
• InChiKey: XCHLUYNMRHJOPP-KWXGWXGXSA-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：
  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：

  Os3(CO)10(pyridine-2-carbaldehyde N-isopropylimine) 以 甲苯 为溶剂， 生成 Os3(CO)10(.sigma-N,μ-2-N',η(2)-(C=N')-pyridine-2-carbaldehyde 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：

  pyridine-2-carbaldehyde N-isopropylimine 、 bis(acetonitrile)decacarbonyltriosmium 以 四氢呋喃 为溶剂， 生成 Os3(CO)10(pyridine-2-carbaldehyde 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

• Synthesis and characterization of two isomers of Os3(CO)10(C5H4N-2-C(H)NR) and the conversion to ortho-metallated HOs3(C5H3N-2-C(H)NR)(CO)9. Part III. X-ray Structure of HOs3(C5H3N-2-C(H)Ni-Pr)(CO)9
  作者：Robert Zoet、Gerard Van Koten、Kees Vrieze、Albert J.M. Duisenberg、Anthony L. Spek

  DOI：10.1016/s0020-1693(00)86014-4

  日期：1988.8

  Os3(CO)10(MeCN)2 reacts at room temperature in MeCN or toluene with R-Pyca† to yield two isomers of Os3(CO)10(R-Pyca) that differ in the bonding of the R-Pyca ligand to the Os3(CO)10 unit. In all cases Os3(CO)10(R-Pyca(4e)) (isomer A; 4a: R = c-Pr, 4b: R = i-Pr, 4c: R = neo-Pent, 4d: R = t-Bu), containing a chelating 4e donating R-Pyca ligand and three OsS bonds, could be isolated. In the case of R

  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。
• Remarkably stable radical anions derived from clusters [HOs3(CO)9(L)], L=ortho-metallated α-diimine: a spectro-electrochemical study and theoretical rationalization
  作者：J Nijhoff、F Hartl、J.W.M van Outersterp、D.J Stufkens、M.J Calhorda、L.F Veiros

  DOI：10.1016/s0022-328x(98)00831-6

  日期：1999.1

  attack of the latter species at yet nonreduced 1 yields an Os–Os bonded cluster dimer [1a–1a]2−. In contrast to the reactivity of 1−, the radical anions of the clusters [HOs3(CO)9(C5H3N-2-C(H)N–iPr)] (2), [HOs3(CO)9(6-CH2–C5H3N-2-C(H)N–iPr)] (3), containing the ortho-metallated ligands o-iPr–PyCa6-X} (X=H, Me}, are substantially more stable. At room temperature in THF, 2− and 3− slowly disproportionate

  团簇的还原[Os 3（CO）10（i Pr-PyCa）]，i Pr–PyCa = σ - N，σ - N'-吡啶-2-甲醛-N-异丙基亚胺，（1）遵循ECEC序列。初始单电子还原步骤产生自由基阴离子1 -这是在低温下稳定的发现上的亚秒时间尺度。在室温下，会形成一个开放结构的自由基阴离子瞬态1a- ，该瞬态瞬间还原为1a 2-。后来物种的攻击仍未减少1产生一个Os-Os键合簇二聚体[ 1a - 1a ] 2-。与此相反的反应性1 - ，簇的自由基阴离子[的HO 3（CO）9（C 5 H ^ 3 N-2-C（H）N-我PR）]（2），[的HO 3（ CO）9（6-CH 2 –C 5 H 3 N-2-C（H）N– i Pr）]（3），含有邻金属化的配体o - i镨的pycA 6-X}（X = H，我}，实质上更稳定的在THF中，室温下。2 -和3 -慢慢不成比例适度稳定双阴离子物种2B和图3c
• 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′
  作者：Jos Nijhoff、Maarten J. Bakker、František Hartl、Derk J. Stufkens

  DOI：10.1016/s0022-328x(98)00955-3

  日期：1999.1

  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.