(C5H4CH3)Mn(η6-cycloheptatriene) | 52308-71-1

• 英文名称: (C5H4CH3)Mn(η6-cycloheptatriene)
• 英文别名: [(η5-methylcyclopentadienyl)Mn(η6-cycloheptatriene)]；[Mn(I)(η5-methylcyclopentadiene)(η6-cycloheptatriene)]；manganese(I)(MeC5H4)(η6-cycloheptatriene
• CAS: 52308-71-1
• 化学式: C₁₃H₁₅Mn
• 分子量: 226.2
• InChiKey: FWOYPEQWADSOMS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 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：

  tritylium hexafluorophosphate 、 (C5H4CH3)Mn(η6-cycloheptatriene) 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 [(η7-C7H7)(η5-CH3C5H4)Mn]PF6
  参考文献：
  名称：

  阳离子环庚三烯基环戊二烯基锰夹心复合物：用高功率 LED 光合作用探索的 Tromancenium

  摘要：

  在这篇文章中，我们重新审视了被忽视和遗忘的阳离子、空气稳定、18 价电子、杂配夹心复合物（环庚三烯基）（环戊二烯基）锰，大约 50 年前由 Fischer 和 Pauson 独立报道。使用先进的高功率 LED 光化学合成，开发了一种方便的快速获取母体复合物和具有烷基、羧甲基、溴和氨基取代基的功能化衍生物的方法。通过一系列光谱技术（1 H/ 13 C/ 55Mn-NMR、IR、UV-vis、HRMS、XRD、XPS、EPR)、循环伏安法 (CV) 和量子化学计算 (DFT) 表明，相比之下，这些锰夹心配合物是独特的茂金属，具有截然不同的化学和物理性质与早期过渡金属的等电子钴鎓盐或（环庚三烯基）（环戊二烯基）夹心配合物相比。在电化学上，所有的三氧化二锰离子在响应 Cp 平台上的取代基的半波或峰值电位下经历化学部分可逆氧化和化学不可逆还原。如母体钍离子示例性所示，在不可逆还原过程中产生的产物在再

  DOI：

  10.1021/acs.organomet.1c00376
• 作为产物：
  描述：

  环庚三烯 、 methylcyclopentadienyl manganese(I) tricarbonyl 以 正庚烷 为溶剂， 反应 0.25h， 生成 (C5H4CH3)Mn(η6-cycloheptatriene)
  参考文献：
  名称：

  阳离子环庚三烯基环戊二烯基锰夹心复合物：用高功率 LED 光合作用探索的 Tromancenium

  摘要：

  在这篇文章中，我们重新审视了被忽视和遗忘的阳离子、空气稳定、18 价电子、杂配夹心复合物（环庚三烯基）（环戊二烯基）锰，大约 50 年前由 Fischer 和 Pauson 独立报道。使用先进的高功率 LED 光化学合成，开发了一种方便的快速获取母体复合物和具有烷基、羧甲基、溴和氨基取代基的功能化衍生物的方法。通过一系列光谱技术（1 H/ 13 C/ 55Mn-NMR、IR、UV-vis、HRMS、XRD、XPS、EPR)、循环伏安法 (CV) 和量子化学计算 (DFT) 表明，相比之下，这些锰夹心配合物是独特的茂金属，具有截然不同的化学和物理性质与早期过渡金属的等电子钴鎓盐或（环庚三烯基）（环戊二烯基）夹心配合物相比。在电化学上，所有的三氧化二锰离子在响应 Cp 平台上的取代基的半波或峰值电位下经历化学部分可逆氧化和化学不可逆还原。如母体钍离子示例性所示，在不可逆还原过程中产生的产物在再

  DOI：

  10.1021/acs.organomet.1c00376

文献信息

• New Access to Homodinuclear Half‐Sandwich Vinylidenemanganese Complexes
  作者：Koushik Venkatesan、Thomas Fox、Helmut W. Schmalle、Heinz Berke

  DOI：10.1002/ejic.200400686

  日期：2005.3

  4-C 4 H 2 S}) and R 2 PCH 2 CH 2 PR 2 (R = Me, Et) at 50 °C for 12 h to yield the corresponding dinuclear complexes in very good yields. These dinuclear tin-substituted vinylidene complexes were further treated with an excess of MeOH to give the corresponding dinuclear parent vinylidene complexes of the type [Mn(MeC 5 H 4 )(R 2 PCH 2 CH 2 PR 2 )=C=C(H)} 2 X}] (X = μ-1,4-C 6 H 4 }, R = Me, 6a; X =

  [Mn(MeC 5 H 4 )(R 2 PCH 2 CH 2 PR 2 )=C=C(SnMe 3 )} 2 X}] ( X = μ-1,4-C 6 H 4 }, R = Me, 2a; X = μ-1,4-C 6 H 4 }, R = Et, 2b; X = μ-1,3 -C 6 H 4 }, R = Me, 3a; X = μ-1,3-C 6 H 4 }, R = Et, 3b; X = μ-4,4-C 6 H 4 -C 6 H 4 }, R = Me, 4a; X = μ-4,4-C 6 H 4 -C 6 H 4 }, R = Et, 4b; X = μ-1,4-C 4 H 2 S }, R = Me, 5a; X = μ-1,4-C 4 H 2 S}, R = Et, 5b) 由[Mn(C 5 H 4 Me) (η 6 -环庚三烯)] 与 0.5 当量。相应的乙炔
• μ-Carbon−Carbon Bonds of Dinuclear Manganese Half-Sandwich Complexes as Electron Reservoirs
  作者：Koushik Venkatesan、Olivier Blacque、Thomas Fox、Montserrat Alfonso、Helmut W. Schmalle、Sohrab Kheradmandan、Heinz Berke

  DOI：10.1021/om049284c

  日期：2005.2.1

  The mononuclear vinylidene complexes of the type Mn(C5H4R')(R"2PCH2CH2PR"(2))(=C= C(R')(SnMe3)) were obtained by the reaction Of Mn(C5H4R')(eta(6)-cycloheptatriene) (R' = H, 1a; CH3, 1b) with 1 equiv of R-1-C drop C-SnMe3 (R-1 = SnMe3, C6H5, C4H3S, C6H4CH3) and R"2PCH2CH2PR"(2) (R" = CH3 (dmpe), C2H5 (depe)) in toluene at 50degreesC for 3 h. The reactions of these tin-substituted complexes with 1 equiv of 1.0 M TBAF yielded the corresponding parent vinylidene species Mn(C5H4R')(R"2PCH2CH2PR"(2))(=C=C(R-1)(H)). Treatment of some of these vinylidene species with 1 equiv of [Cp2Fe][PF6] led to the oxidative coupling product [(C5H4R')(R"2PCH2CH2PR"(2))MndropC-CHR1-CHR1-CdropMn(R"2PCH2CH2PR"(2))(C5H4R')]-[PF6](2) (R' = CH3, R" = CH3, R-1 = H; R'= CH3, R" = CH3, R-1 = C6H5; R' = CH3, R" = CH3, R-1 = C4H3S; R' = H, R" = C2H5, R-1 = H; R' = H, R" = C2H5, R-1 = C6H5; R' = H, R" C2H5, R-1 = C4H3S). In some cases these products of oxidative coupling, [(C5H4R')(R"2PCH2CH2-PR"(2))Mn drop C-CHR1-CHR1-CdropMn(R"2PCH2CH2PR"(2))(C5H4R')][PF6](2), were accompanied by formation of dinuclear complexes of the type [(C5H4R')(R"2PCH2CH2PR"(2))MndropC-CR1=CR1-CdropMn(R"2PCH2CH2PR"(2))(C5H4R')][PF6](2) and of the cationic carbyne complexes [(C5H4R')(R"2PCH2CH2PR"(2))MndropC-CH2R1] [PF6] obtained by proton transfer. Reduction of these dinuclear complexes with CP2*Co yielded back the corresponding mononuclear precursor complexes involving a reductive decoupling process. Both the reductive coupling and the oxidative coupling are fully reversible, which is supported by DFT calculations. The mononuclear and the dinuclear compounds were characterized by NMR, IR, and cyclic voltammetric studies. X-ray diffraction studies have been performed on complexes 3a, 11, 13a, 15a, and 22b.
• Carbon−Carbon Bonds of Manganese Half-Sandwich Complexes for Electron Reservoir Functions
  作者：Koushik Venkatesan、Olivier Blacque、Thomas Fox、Montserrat Alfonso、Helmut W. Schmalle、Heinz Berke

  DOI：10.1021/om034237q

  日期：2004.3.1

  Vinylidene species of the type Mn(C5H4CH3)[(H3C)(2)PCH2CH2P(CH3)(2)](=C=(CRR2)-R-1) (R-1 = R-2 = H; RI = H, R2 = Ph) can be fully reversibly coupled to yield the dinuclear complexes [(C5H4CH3)(dmpe)Mnequivalent to CC(R-1)(R-2)C(R-1)(R-2)Cequivalent toMn(dmpe)(C5H4CH3)][PF6](2) (R-1, R-2 = H; R-1 = H, R-2 = Ph) by an oxidation/reduction cycle involving formation and cleavage of a C-C sigma bond.
• Synthetic Access to Half-Sandwich Manganese C₄ Cumulenic Complexes
  作者：Koushik Venkatesan、Olivier Blacque、Thomas Fox、Montserrat Alfonso、Helmut W. Schmalle、Heinz Berke

  DOI：10.1021/om049551e

  日期：2004.9.1

  The vinylalkynyl complexes Mn(C5H4R')(R"2PCH2CH2PR"(2))(=C CSnPh3C=-CSnPh3) (5, 6) were obtained in good yields by treatment of Mn(C5H4R')(eta(6)-cycloheptatriene) (R' = H (1a), Me (1b)) with 1 equiv of Ph(3)SnCdropCCdropCSnPh(3) and R"2PCH2CH2PR"(2) (R" = CH3 (dmpe), C2H5 (depe)). The theoretically characterized (DFT) C-4 cumulenic species Mn(C5H4R')(R"2PCH2CH2PR"(2))=C=C=C C(SnPh3)(2)} (7, 8) were obtained by photolysis of the tin-substituted vinylalkynyl complexes 5 and 6. Subsequently 7 and 8 could be converted into the parent cumulenic species Mn(C5H4R')(R"2PCH2CH2PR"(2))=C=C=C=C(H)(2)} (9, 10) by reacting complexes 7 and 8 with TBAF (5% H2O) at -40 degreesC. The difference in the thermodynamic stabilities between the complexes 7 and 8 and complexes 9 and 10 was traced by DFT calculations using Mn(C5H5)(dHpe)=C=C=C=C(SnMe3)(2)} (4-H) and Mn(C5H5)(dHpe)=C=C=C=CH2} (9-H) as model complexes. Treatment of the vinylalkynyl complex with an excess of MeOH led to the formation of a dinuclear complex with a C-8 chain between two manganese centers. The cumulenic complexes and the vinylalkynyl complexes were characterized by NMR and vibrational spectroscopy and elemental analyses. An X-ray diffraction study has been performed on complex 4b.