(1,2-bis(dimethylphosphino)ethane)(η(5)-methylcyclopentadienyl)(phenylvinylidene)manganese(I) | 223424-74-6

• 英文名称: (1,2-bis(dimethylphosphino)ethane)(η(5)-methylcyclopentadienyl)(phenylvinylidene)manganese(I)
• 英文别名: [Mn(η5-methylcyclopentadienyl)(bis(1,2-dimethylphosphino)ethane)(CC(H)(Ph))]；[Mn(I)(η5-methylcyclopentadiene)(bis(dimethylphosphino)ethane)(CCH(Ph))]；[Mn(η5-methylcyclopentadienyl)(dmpe)(CC(H)(Ph))]
• CAS: 223424-74-6
• 化学式: C₂₀H₂₉MnP₂
• 分子量: 386.336
• InChiKey: YHTRIJWHXGIKBL-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：

  ferrocenium(III) tetrafluoroborate 、 (1,2-bis(dimethylphosphino)ethane)(η(5)-methylcyclopentadienyl)(phenylvinylidene)manganese(I) 以 二氯甲烷 为溶剂， 以85%的产率得到[(1,2-bis(dimethylphosphino)ethane)(η(5)-methylcyclopentadienyl)(phenylethynyl)manganese(III)] tetrafluoroborate
  参考文献：
  名称：

  通过锰茂化合物生成单和双（炔基）锰（II）和锰（III）配合物的多功能途径

  摘要：

  以锰茂（RC 5 H 4）2 Mn（R = H，Me）为起始原料，顺磁性d 5半三明治复合物（RC 5 H 4）Mn（dmpe）（C⋮CR'）（dmpe = 1， 1,2-双（二甲基膦基）乙烷; R = Me中，R '=苯基，1A ; R = Me中，R'=森达3，图2a ; R = H，R '=苯基，1B ; R = H，R'=森达3，图2b）已经制备通过与终端或SnMe反应3个取代的乙炔和DMPE。衍生物1a和2a可以分离，而1b和2b已经鉴定出与双（dmpe）双（乙炔）锰物种3（R'= Ph）和4（R'= SiMe 3）的混合物。当锰茂与dmpe和相应的乙炔以1：2：2的比例反应时，后一种化合物作为唯一产物获得。1a和2a可以可逆地氧化为相应的阳离子Mn（III）络合物[（MeC 5 H 4）Mn（dmpe）（C⋮CR'）] [BF 4 ]（R'= Ph，[ 1a ] + ; R '=

  DOI：

  10.1021/om9810549
• 作为产物：
  描述：

  [Mn(η5-methylcyclopentadienyl)(bis(1,2-dimethylphosphino)ethane)(CC(H)Ph)]2[PF6]2 在 (C₅(CH₃)5)2Co 作用下， 以 二氯甲烷 为溶剂， 以99%的产率得到(1,2-bis(dimethylphosphino)ethane)(η(5)-methylcyclopentadienyl)(phenylvinylidene)manganese(I)
  参考文献：
  名称：

  μ-Carbon−Carbon Bonds of Dinuclear Manganese Half-Sandwich Complexes as Electron Reservoirs

  摘要：

  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.

  DOI：

  10.1021/om049284c

文献信息

• 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.