[(η(5)-Me-thiophene)Mn(CO)3](BF4) | 199858-88-3

• 英文名称: [(η(5)-Me-thiophene)Mn(CO)3](BF4)
• CAS: 199858-88-3
• 化学式: BF₄*C₈H₆MnO₃S
• 分子量: 323.942
• InChiKey: JZRSRUBPEZAXTM-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：

  [(η(5)-Me-thiophene)Mn(CO)3](BF4) 、 一氧化碳 在 cobaltocene 作用下， 以 二氯甲烷 为溶剂， 以72%的产率得到
  参考文献：
  名称：

  Models for the Homogeneous Hydrodesulfurization of Thiophenes:  Manganese-Mediated Carbon−Sulfur Bond Cleavage and Hydrogenation Reactions

  摘要：

  Chemical reduction of a series of (eta(5)-thiophene)Mn(CO)(3)(+) complexes (3a-d) under an atmosphere of CO affords dimanganese metallathiacyclic complexes (4a-d), which have a Mn(CO)(4) moiety regioselectively inserted into a C-S bond. Reaction of 4 with H-2, the rate of which is strongly influenced by substituents on the thiophene ring, leads to hydrogenolysis of the Mn-C sigma-bond and formation of (OC)(3)Mn(mu-H)(mu-SCRCHCHCHR')Mn(CO)(3) (8; R, R' = H, Me), which contains bridging hydride and thiolate ligands and a Mn-Mn bond. The addition of PhMgBr to 3 occurs at the sulfur to give zwitterionic complexes (6a-c, 14), which undergo regioselective hydrogenolysis of a C-S bond and, in some cases, partial desulfurization with concomitant formation of (OC)(4)Mn(mu-H)(mu-SPh)Mn(CO)(4) (5a). Crystal structures are reported for complexes 4b,d, 5a, 8d, 10, 12c, and 14b,c. It is suggested that the reactions reported herein may be relevant to the general problem of hydrodesulfurization (HDS) of thiophenic molecules.

  DOI：

  10.1021/om970822d
• 作为产物：
  描述：

  五羰基溴化锰(I) 、 3-甲基噻吩 、 silver tetrafluoroborate 以 二氯甲烷 为溶剂， 以68%的产率得到[(η(5)-Me-thiophene)Mn(CO)3](BF4)
  参考文献：
  名称：

  Models for the Homogeneous Hydrodesulfurization of Thiophenes:  Manganese-Mediated Carbon−Sulfur Bond Cleavage and Hydrogenation Reactions

  摘要：

  Chemical reduction of a series of (eta(5)-thiophene)Mn(CO)(3)(+) complexes (3a-d) under an atmosphere of CO affords dimanganese metallathiacyclic complexes (4a-d), which have a Mn(CO)(4) moiety regioselectively inserted into a C-S bond. Reaction of 4 with H-2, the rate of which is strongly influenced by substituents on the thiophene ring, leads to hydrogenolysis of the Mn-C sigma-bond and formation of (OC)(3)Mn(mu-H)(mu-SCRCHCHCHR')Mn(CO)(3) (8; R, R' = H, Me), which contains bridging hydride and thiolate ligands and a Mn-Mn bond. The addition of PhMgBr to 3 occurs at the sulfur to give zwitterionic complexes (6a-c, 14), which undergo regioselective hydrogenolysis of a C-S bond and, in some cases, partial desulfurization with concomitant formation of (OC)(4)Mn(mu-H)(mu-SPh)Mn(CO)(4) (5a). Crystal structures are reported for complexes 4b,d, 5a, 8d, 10, 12c, and 14b,c. It is suggested that the reactions reported herein may be relevant to the general problem of hydrodesulfurization (HDS) of thiophenic molecules.

  DOI：

  10.1021/om970822d