HOs3(CO)9(.mu-C29H23O3P2) | 1252013-24-3

• 英文名称: HOs3(CO)9(.mu-C29H23O3P2)
• CAS: 1252013-24-3
• 化学式: C₃₈H₂₄O₁₂Os₃P₂
• 分子量: 1305.15
• InChiKey: CIYKWLLBGBYXNP-HPVDVEBPSA-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：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  一氧化碳 、 HOs3(CO)9(.mu-C29H23O3P2) 、 HOs3(CO)9(μ-C29H23O3P2) 以 苯 为溶剂， 生成 1,2-Os3(CO)10(3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone) 、 1,2-Os3(CO)10(3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone)
  参考文献：
  名称：

  Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P–C bond cleavage in the unsaturated cluster 1,1-Os3(CO)9(bmf): Synthesis and X-ray diffraction structures of the isomeric Os3(CO)10(bmf) clusters and HOs3(CO)8(μ-C6H4)[μ-PhPCC(Ph2P)CH(OMe)OC(O)]

  摘要：

  The labile cluster 1,2-Os-3(CO)(10)(MeCN)(2) (1) reacts with the chiral diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) to furnish 1,2-Os-3(CO)(10)(bmf) (2a) in high yield. Heating cluster 2a over the temperature range 358-383 K under CO leads to isomerization of the bmf ligand and formation of the diphosphine-chelated cluster 1,1-Os-3(CO)(10)(bmf) (2b) and an equilibrium mixture consisting of 2a and 2b in a 15:85 ratio. Extended thermolysis of an equilibrium mixture of Os-3(CO)(10)(bmf) is accompanied by CO loss and ortho-metalation of an aryl ring to afford an inseparable mixture of three diastereomeric hydride clusters HOs3(CO)(9)(C29H23O3P2) (3a-c). Thermolysis of HOs3 (CO)(9)(C29H23O3P2) (3a-c) in refluxing toluene leads to P-C bond cleavage and formation of the benzyne-substituted clusters HOs3(CO)(8)(mu-C6H4)(mu-C23H19O3P2) (4a,b) as a 4:1 mixture of diastereomers. The unequivocal identity of the major benzyne-substituted cluster has been determined by X-ray diffraction analysis, where the activation of one of the phenyl groups situated a to the furanone carbonyl group in the bmf ligand has been established. The isomerization and activation of the bmf ligand are contrasted with other Os-3(CO)(10)(diphosphine) derivatives prepared by our groups. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2010.07.003
• 作为产物：
  描述：

  1,2-Os3(CO)10(3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone) 、 1,2-Os3(CO)10(3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone) 以 氘代苯 为溶剂， 生成 HOs3(CO)9(.mu-C29H23O3P2) 、 HOs3(CO)9(μ-C29H23O3P2)
  参考文献：
  名称：

  Isomerization of the diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) at a triosmium cluster and P–C bond cleavage in the unsaturated cluster 1,1-Os3(CO)9(bmf): Synthesis and X-ray diffraction structures of the isomeric Os3(CO)10(bmf) clusters and HOs3(CO)8(μ-C6H4)[μ-PhPCC(Ph2P)CH(OMe)OC(O)]

  摘要：

  The labile cluster 1,2-Os-3(CO)(10)(MeCN)(2) (1) reacts with the chiral diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) to furnish 1,2-Os-3(CO)(10)(bmf) (2a) in high yield. Heating cluster 2a over the temperature range 358-383 K under CO leads to isomerization of the bmf ligand and formation of the diphosphine-chelated cluster 1,1-Os-3(CO)(10)(bmf) (2b) and an equilibrium mixture consisting of 2a and 2b in a 15:85 ratio. Extended thermolysis of an equilibrium mixture of Os-3(CO)(10)(bmf) is accompanied by CO loss and ortho-metalation of an aryl ring to afford an inseparable mixture of three diastereomeric hydride clusters HOs3(CO)(9)(C29H23O3P2) (3a-c). Thermolysis of HOs3 (CO)(9)(C29H23O3P2) (3a-c) in refluxing toluene leads to P-C bond cleavage and formation of the benzyne-substituted clusters HOs3(CO)(8)(mu-C6H4)(mu-C23H19O3P2) (4a,b) as a 4:1 mixture of diastereomers. The unequivocal identity of the major benzyne-substituted cluster has been determined by X-ray diffraction analysis, where the activation of one of the phenyl groups situated a to the furanone carbonyl group in the bmf ligand has been established. The isomerization and activation of the bmf ligand are contrasted with other Os-3(CO)(10)(diphosphine) derivatives prepared by our groups. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2010.07.003