[Os3(CO)8(triphenylphosphine)2(μ-dppm)] | 150676-41-8

• 英文名称: [Os3(CO)8(triphenylphosphine)2(μ-dppm)]
• 英文别名: [Os₃(CO)₈(triphenylphosphine)₂(μ-dppm)]；[Os₃(CO)₈(PPh₃)₂(μ-dppm)]
• CAS: 150676-41-8
• 化学式: C₆₉H₅₂O₈Os₃P₄
• 分子量: 1703.66
• InChiKey: ASECWKUIXFEJPC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 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：

  [Os3(CO)8(triphenylphosphine)2(μ-dppm)] 以 甲苯 为溶剂， 反应 0.5h， 以52%的产率得到[Os₃(CO)₉(triphenylphosphine)(μ-dppm)]
  参考文献：
  名称：

  A comparative study of the reactivity of the lightly stabilized cluster [Os3(CO)8{μ3-Ph2PCH2P(Ph)C6H4}(μ-H)] towards tri(2-thienyl)-, tri(2-furyl)- and triphenyl-phosphine

  摘要：

  Reactions of the lightly stabilized triosmium cluster [Os-3(CO)(8){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)] with tri(2-thienyl)phosphine (PTh3) and tri(2-furyl)phosphine (PFu(3)) are described and compared to analogous reactions with PPh3. At room temperature, a number of products are isolated: [Os-3(CO)(10)(mu-dppm)] from CO addition, [Os-3(CO)(8)(PR3){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)] from phosphine addition, [Os-3(CO)(9)(PR3)(mu-dppm)] from phosphine and CO addition and [Os-3(CO)(8)(PR3)(2)(mu-dppm)] from addition of two equivalents of phosphine. The latter are shown by NMR and X-ray diffraction to exist as 1,2-isomers, whereby one phosphine is bound to the non-dppm-substituted center and the second shares an osmium atom with one end of the diphosphine. Heating 1,2-[Os-3(CO)(8)(PTh3)(2)(mu-dppm)] at 100 degrees C results in its clean isomerization to the 1,1-isomer in which both monodentate phosphines are located on the same osmium atom. Prolonged heating of [Os-3(CO)(8)(PR3)(2)(mu-dppm)] (R = Th, Ph) at 110 degrees C gives [Os-3(CO)(9)(PR3)(mu-dppm)] and the new lightly stabilized clusters [Os-3(CO)(7)(PR3){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)], the latter being formed by loss of phosphine and CO with concurrent metalation of a phenyl ring. Heating [Os-3(CO)(8)(PFu(3))(2)(mu-dppm)] at 110 degrees C gives [Os-3(CO)(9)(PFu(3))(mu-dppm)] together with the carbon-phosphorus bond cleavage products [Os-3(CO)(7)(mu-PFu(2))(mu(3)-eta(2)-C4H2O)(mu-H)(mu-dppm)] and [Os-3(CO)(7)(mu-PFu(2))(mu(3)-eta(2)-C6H3CH3)(mu-H)(mu-dppm)]. All new compounds were characterized by analytical and spectroscopic techniques together with single crystal X-ray diffraction analysis of nine clusters. Density functional theory (DFT) calculations have been carried out on isomers of [Os-3(CO)(8)(PR3)(2)(mu-dppm)] in order to understand the observed isomer ratios. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.08.027
• 作为产物：
  描述：

  三苯基膦 、 [(μ-H)(CO)8(Ph2PCH2P(Ph)C6H4)] 以 甲苯 为溶剂， 以27%的产率得到[Os3(CO)8(triphenylphosphine)2(μ-dppm)]
  参考文献：
  名称：

  不饱和tri簇[Os 3 H（CO）8 {Ph 2 PCH 2 P（Ph）C 6 H 4 }]和[Os 3 H（CO）8 {Ph 2 PC（CH 2）P（Ph） C 6 H 4 }]与膦和亚磷酸酯；[Os 3 H（CO）8 {Ph 2 PCH 2 P（Ph）C 6 H 4 }（PPr i 3）]，[Os 3（CO）8（Ph 2 PCH 2 PPh ）的晶体结构2）{P（OMe）3 } 2 ]和[Os 3（CO）8（Ph 2 PCH 2 PPh 2）（PPh 3）2 ]

  摘要：

  [Os 3（µ-H）（CO）8 {µ-Ph 2 PCH 2 P（Ph）C 6 H 4 }] 1a和[Os 3（µ-H）（CO）8 {µs具有两个电子给体配体的-Ph 2 PC（CH 2）P（Ph）C 6 H 4 }] 1b得到饱和簇[Os 3（µ-H）（CO）8 {µ-Ph 2 PCH 2 P（ Ph）C 6 H 4 } L] [L = CO 2a或PR 3或P（OR）33（R = Me，Et，Pr i，Bu或Ph）]，[Os 3（µ-H）（CO）8 {µ-Ph 2 PC（CH 2）P（Ph）C 6 H 4 } L] （L ＝ CO 2b）和[Os 3（CO）8（dppm）L 2 ] 4 [dppm ＝ Ph 2 PCH 2 PPh 2；L ＝ CO，PR 3或P（OR）3 ]。取决于配体L，观察到配合物4的两种不同的异构体。所有产物已经通过IR和NMR光谱表征。[Os 3 H（CO）的结构8

  DOI：

  10.1039/dt9930001671