[(η(6)-dibenzothiophene)Mn(CO)3]BF4 | 158446-08-3

• 英文名称: [(η(6)-dibenzothiophene)Mn(CO)3]BF4
• 英文别名: [(η(6)-dibenzothiphene)Mn(CO)3]BF4
• CAS: 158446-08-3
• 化学式: BF₄*C₁₅H₈MnO₃S
• 分子量: 410.035
• InChiKey: LLTBOKQJZFHTAB-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：

  [(η(6)-dibenzothiophene)Mn(CO)3]BF4 在 cobaltocene or Na/Hg 作用下， 以 二氯甲烷 为溶剂， 以10%的产率得到
  参考文献：
  名称：

  Insertion of manganese into a C–S bond of dibenzothiophene: a model for homogeneous hydrodesulfurization

  摘要：

  Mn(CO)3+ 与二苯并噻吩碳环的配位激活了 CâS 键的还原裂解，产生了一种新的四锰金属硫环 5，它与 H2 反应形成了一种含有桥接氢化物和硫酸盐配体的二锰配合物 9；5 的甲基化和随后的氢化导致二苯并噻吩脱硫并形成 [Mn(CO)5(SMe)]。

  DOI：

  10.1039/a706096c

文献信息

• Activation of the Carbon−Sulfur Bonds in Benzothiophenes by Precoordination of Transition Metals to the Carbocyclic Ring
  作者：Conor A. Dullaghan、Xiao Zhang、David L. Greene、Gene B. Carpenter、Dwight A. Sweigart、Chiara Camiletti、Edward Rajaseelan

  DOI：10.1021/om9802865

  日期：1998.7.1

  regiospecific cleavage of the olefinic C−S bond rather than the aryl C−S bond, which is likely a consequence of steric congestion that would exist if insertion had occurred at the latter site. The X-ray structures of the metallathiacycles (η6-BT·Pt(PPh3)2}Mn(CO)3+ and (η6-BT·Pt(PPh3)2}FeCp+ are reported. The complexes (η5-2,5-dimethylthiophene)Mn(CO)3+ and (η6-dibenzothiophene)Mn(CO)3+ also undergo

  亲电过渡金属片段的协调，ML Ñ，以苯并噻吩（BT）的碳环，以形式（η 6 -BT）ML Ñ米+通过弱亲核试剂Pt（PPh 3）3激活C-S键裂解，并伴随插入Pt（PPh 3）2。形成所得metallathiacyclic插入产品，（η率6 -BT·铂（PPH 3）2 } ML Ñ米+取决于金属碎片，其顺序为ML n = Ru（C 6 Me 6）2 +，Mn（CO）3 + > FeCp +，RuCp + Cr（CO）3，如果不存在，则不会发生反应ML n激活基团。所有未取代的苯并噻吩配合物都经历了烯烃C-S键而不是芳基C-S键的区域特异性裂解，这很可能是空间拥挤的结果，如果在后面的位点发生插入，则会存在空间拥堵。所述metallathiacycles （η的X射线结构6 -BT·铂（PPH 3）2 }的Mn（CO）3+和（η 6 -BT·铂（PPH 3）2 } FeCp +报告。该复合物（η
• Regioselectivity in the nucleophilic functionalization of dibenzofuran, dibenzothiophene and xanthene complexes of Mn(CO)3+
  作者：Ivana Verona、James P. Gutheil、Robert D. Pike、Gene B. Carpenter

  DOI：10.1016/s0022-328x(96)06347-4

  日期：1996.11

  The cationic complexes [(eta(6)-DBF)Mn(CO)(3)]BF4, [(eta(6)-DBT)Mn(CO)(3)]BF4 and [(eta(6)-XAN)Mn(CO)(3)]PF6 (DBF = dibenzofuran, DBT = dibenzothiophene, XAN = xanthene) are prepared. These species react with carbon-based nucleophiles to form exo-substituted cyclohexadienyl complexes, Addition is found exclusively at carbons 1 and 4. The C(1)-functionalized regioisomer predominates, especially for the DBF and XAN complexes, for which 90 to > 95% selectivity is found with stabilized nucleophiles. Preference for C(1) is greatly reduced for unstabilized magnesium and lithium nucleophiles. The origin of this selectivity is discussed. Loss of the aromatic ring from the cationic complexes in the presence of CH3CN is found to be extremely facile for the DBF and DBT complexes owing to increased ease of ring slippage. Second-order rate constants for the displacement reactions with CH3CN are 4.6 +/- 0.6 x 10(-5) M(-1) s(-1) (DBF complex, 25 degrees C), 4.4 +/- 1.0 x 10(-5) M(-1) s(-1) (DBT complex, 25 degrees C) and about 1.0 x 10(-5) M(-1) s(-1) (XAN complex, 60 degrees C). A crystal structure is presented for the hydride adduct of the DBF complex, [(eta(5)-C12H9O)Mn(CO)(3)]: space group P2(1)/c, a = 15.301(2), b = 6.4422(12), c = 12.988(2) Angstrom, beta = 90.888(13)degrees, V = 1280.1(3) Angstrom(3), Z = 4, D-calc = 1.599 Mg m(-3), R = 0.0410 and wR2 = 0.0945 on 2446 reflections with F-2 > 4.0 sigma(F-2).