MnI2(THF)2 | 73949-72-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: MnI2(THF)2
• CAS: 73949-72-1
• 化学式: C₈H₁₆I₂MnO₂
• 分子量: 452.961
• InChiKey: KKXREHMKZSERTD-UHFFFAOYSA-L

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：

  MnI2(THF)2 、 [((3-Me3C)(1-Me3Si)3C5H3)2Mg] 以 四氢呋喃 为溶剂， 以68%的产率得到[((3-Me3C)(1-Me3Si)3C5H3)2Mn]
  参考文献：
  名称：

  Spin Equilibria in Monomeric Manganocenes: Solid-State Magnetic and EXAFS Studies

  摘要：

  Magnetic susceptibility measurements and X-ray data confirm that tert-butyl-substituted manganocenes [(Me3C)(n)C5H5-n](2)Mn (n=1, 2) follow the trend previously observed with the methylated manganocenes; that is, electron-donating groups attached to the Cp ring stabilize the low-spin (LS) electronic ground state relative to Cp2Mn and exhibit higher spin-crossover (SCO) temperatures. However, introducing three CMe3 groups on each ring gives a temperature-invariant high-spin (HS) state manganocene. The origin of the high-spin state in [1,2,4-(Me3C)(3)C5H2](2)Mn is due to the significant bulk of the [1,2,4-(Me3C)(3)C5H2](-) ligand, which is sufficient to generate severe inter-ring steric strain that prevents the realization of the low-spin state. Interestingly, the spin transition in [1,3-(Me3C)(2)C5H3](2)Mn is accompanied by a phase transition resulting in a significant irreversible hysteresis (Delta T-c=16 K). This structural transition was also observed by extended X-ray absorption fine-structure (EXAFS) measurements. Magnetic susceptibility studies and X-ray diffraction data on SiMe3-substituted manganocenes [(Me3Si)(n)C5H5-n](2)Mn (n=1, 2, 3) show high-spin configurations in these cases. Although tetra- and hexasubstituted manganocenes are high-spin at all accessible temperatures, the disubstituted manganocenes exhibit a small low-spin admixture at low temperature. In this respect it behaves similarily to [(Me3C)-(Me3Si)C5H3](2)Mn, which has a constant low-spin admixture up to 90 K and then gradually converts to high-spin. Thermal spin-trapping can be observed for [(Me3C)(Me3Si)C5H3](2)Mn on rapid cooling.

  DOI：

  10.1021/om800922j

文献信息

• Two-coordinate, homoleptic manganese(ii) primary terphenyl amido complexes: the effects of secondary coordination on geometry and Lewis base complexation
  作者：Chengbao Ni、Brian Rekken、James C. Fettinger、Gary J. Long、Philip P. Power

  DOI：10.1039/b911978g

  日期：——

  The synthesis and characterization of the mononuclear manganese primary amido complex MnN(H)Ar(#)}(2) (), its Lewis base adducts MnN(H)Ar(#)}(2)(L) (Ar(#) = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-Me(3))(2); L = THF (), and C(5)H(5)N ()), and MnN(H)Ar*}(2) () (Ar* = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-(i)Pr(3))(2)) are described. Complex was prepared by the reaction of MnCl(2) with two equivalents of LiN(H)Ar(#) in

  单核锰伯酰胺配合物Mn N（H）Ar（＃）}（2）（）的路易斯碱加合物Mn N（H）Ar（＃）}（2）（L）的合成和表征Ar（＃）= C（6）H（3）-2,6-（C（6）H（2）-2,4,6-Me（3））（2）; L = THF（），和C（5）H（5）N（））和Mn N（H）Ar *}（2）（）（Ar * = C（6）H（3）-2,6-（C（6）描述了H（2）-2,4,6-（i）Pr（3））（2））。通过使MnCl（2）与两当量的LiN（H）Ar（＃）在苯中反应制备配合物。X射线晶体学表明，它具有准两坐标的强弯曲几何形状，其中Mn-N = 1.979（3）A，N-Mn-N = 138.19（9）度，并且具有次级MnC（芳环）相互作用。相反，通过与上述相同的方法制备的络合物具有几乎线性的几何结构，宽的N-Mn-N角为176.1（2）度。该配合物是锰的第一个结构特征的均配的伯氨基酰胺衍生
• Ein neuartiger Zugang zu reduzierten Polyoxomolybdaten mit komplexen Gegenionen - Synthese und Struktur von [Mn(CH₃OH)₆][Mo₈O₁₆(OCH₃)₈(C₂O₄)]
  作者：Anke Sterzik、Helmar Görls、Eike T. Spielberg、Winfried Plass、Wolfgang Imhof

  DOI：10.1002/zaac.200801200

  日期：2009.9

  The tetranuclear compound [Mo2(O2C-tBu)3]2(μ-C2O4) (1) that is prepared from [Mo2(O2C-tBu)3]4 and oxalic acid, was reacted with MnI2·2THF to form the polyoxomolybdate compound [Mn(CH3OH)6] [Mo8O16(OCH3)8(C2O4)] (2) in a complex redox reaction. Crystals of 2 were analyzed by single-crystal X-ray diffraction showing a octanuclear polyoxomolybdate dianion in which the Mo=O moieties are alternately connected

  由[Mo2(O2C-tBu)3]4和草酸制备的四核化合物[Mo2(O2C-tBu)3]2(μ-C2O4)(1)与MnI2·2THF反应生成聚氧钼酸盐化合物[Mn(CH3OH)6] [Mo8O16(OCH3)8( )] (2) 在复杂的氧化还原反应中。2 的晶体通过单晶 X 射线衍射分析，显示八核多氧钼酸二价阴离子，其中 Mo=O 部分通过 μ-氧代和 μ-甲氧代单元交替连接。2 中的电荷平衡是通过由甲醇配体八面体配位的锰 (II) 阳离子实现的。晶体结构主要由与锰配位的 O-H···O 型甲醇分子以及晶格中其他甲醇分子的强氢键相互作用决定。
• The preparation of new manganese(II) isocyanide complexes, MnI2(CNBut)n (n=1, 1.5, 2) and the mixed isocyanide/tertiary-phosphine complex MnI2(PPh3)(CNBut)2. The isolation and X-ray crystallographic characterisation of the MnI/MnII mixed-valence isomeric complexes [Mn(CNBut)6][MnI3(PPh3)] and [Mn(CNBut)5(PPh3)][MnI3(CNBut)]
  作者：Stephen M. Godfrey、Qing Li Guang、Charles A. McAuliffe、Peter T. Ndifon、Robin G. Pritchard

  DOI：10.1016/s0020-1693(00)92344-2

  日期：1992.8

  The complexes MnI2(CNBut)n (n = 1, 1.5 and 2) have been prepared by reaction of MnI2 or MnI2Ln (L = PPh3, THF, n = 2; L = (4-CH3C6H4)3p, n = 1.5) with CNBut in toluene. The reaction of MnI2(PPh3)2 with CNBut in n-pentane slurry gives the complex of formula MnI2(PPh3)(CNBut)2. When MnI2(PPh3)2 reacts with an excess of CNBut in toluene, red-orange crystals of [Mn(CNBut)5(PPh3)][MnI3(CNBut)] and yellow crystals of [Mn(CNBUt)6][MnI3(PPh3)] are formed. X-ray diffraction studies of the two types of crystal show them to have the ion-pair structures. IR studies suggest that in the MnI2(CNBut)n complexes the Mn-C bond is predominantly of sigma-character, whereas in the mixed phosphine/isocyanide derivatives the Mn-C bond is predominantly of pi-character.
• Closing the Gap: Preparation and Characterization of the First Half-Open and Open Manganocene Complexes
  作者：Matthias Reiners、Dirk Baabe、Matthias Freytag、Peter G. Jones、Marc D. Walter

  DOI：10.1021/acs.organomet.6b00281

  日期：2016.6.13

  The first preparations of half-open and open manganocenes were accomplished. Treatment of KPdl' (Pdl' = 2,4-(Me3C)(2)C5H5)) with [(eta(5)-Cp")Mn(thf)(mu-I)}(2)] (Cp" = 1,2,4-(Me3C)(3)C5H2) and MnI2(thf)(2) resulted in the formation of [(eta(5)-Cp")Mn(Pdl')] (2) and [(Pdl')(2)Mn] (4), respectively. Both compounds adopt a high-spin (S = 5/2) ground state. Maximum spin states are rather unusual for pentadienyl complexes, since these ligands, generally stabilize transition metal complexes in their low-spin state. In addition, the electronic structure of 2 was compared to its closed analogue [(eta(5)-Cp")Mn(eta(5)-Cp')] (Cp' = 1,3-(Me3C)(2)C5H3), which also adopts the high-spin configuration because of steric hindrance destabilizing the electronically more favorable low spin state. Reaction of KPdl' with [(C5H5)(2)Mn] yields the trimetallic compound [(eta(5)-Pdl')Mn(eta(5)-C5H5)]}(2)Mn] (5) concomitant with the formation of 2,4,7,9-tetra-tert-butyl-1,3,7,9-decatetraene (Pdl'(2)), indicating reduction of two Mn atoms. Solid-state magnetic susceptibility studies and density functional theory computations suggest that the electronic structure in 5 is best described as two diamagnetic (S = 0) [(eta(5)-Pdl')Mn(eta(5)-C5H5)]Mn-(I) anions, each being coordinated to a central Mn(II) cation with a high-spin (S = 5/2) configuration.