cyclopentadienylmolybdenum(II)(η-allyl)(supine-ηbutadiene) | 189517-98-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: cyclopentadienylmolybdenum(II)(η-allyl)(supine-ηbutadiene)
• 英文别名: CpMo(prone-η-C3H5)(s-cis-supine-η-C4H6)；buta-1,3-diene;cyclopenta-1,3-diene;molybdenum(2+);prop-1-ene
• CAS: 189517-98-4；189517-99-5；189381-85-9
• 化学式: C₁₂H₁₆Mo
• 分子量: 256.199
• InChiKey: OWAXJEJUGPBGOT-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 hexafluorophosphate 、 cyclopentadienylmolybdenum(II)(η-allyl)(supine-ηbutadiene) 以 二氯甲烷 为溶剂， 以60%的产率得到cyclopentadienylmolybdenum(III)(supine-η-allyl)(supine-ηbutadiene) hexafluorophosphate
  参考文献：
  名称：

  含有二烯和烯丙基配体的环戊二烯基钼 (II) 和 -(III) 配合物。1. 一对氧化还原相关有机金属配合物的异构偏好和异构化率

  摘要：

  用 1 当量的烯丙基溴化镁处理 CpMoCl2(η-C4H6) (1) 产生双核复合物 [CpMo(η-C4H6)(μ-Br)]2 (2,major) 和 Cp2Mo2(η-C4H6)2(μ -Br)(μ-Cl)（3，次要）。化合物 2 和 3 的固溶体在固态中采用反几何，如 X 射线晶体学所示，而通过 1 H-NMR 光谱在苯溶液中观察到反和顺异构体。1 与 2 当量的烯丙基溴化镁反应生成 [CpMo(η-C3H5)(η-C4H6)] 作为主要 (98%, 4a) 和次要 (2%, 4b) 异构体的平衡混合物。NOE-NMR 研究表明主要异构体 4a 的 CpMo(prone-C3H5)(supine-C4H6) 取向，通过 X 射线晶体学也发现它在固态中。1H-NMR 化学位移表明 4b 的取向为 CpMo(supine-C3H5)(supine-C4H6)。在二氯甲烷中用六氟磷酸二茂铁氧化

  DOI：

  10.1021/ja964078k
• 作为产物：
  描述：

  cyclopentadienylmolybdenum(III)(supine-η-allyl)(supine-ηbutadiene) hexafluorophosphate 在 cobaltocene 作用下， 以 氘代苯 为溶剂， 生成 cyclopentadienylmolybdenum(II)(η-allyl)(supine-ηbutadiene)
  参考文献：
  名称：

  Cyclopentadienylmolybdenum(II) and -(III) Complexes Containing Diene and Allyl Ligands. 2. Comparative Reactivity of the Isomeric Complexes CpMo(η-C₃H₅)(η-C₄H₆) with Either supine or prone Allyl and Either s-cis (Supine) or s-trans Butadiene Ligands toward Protons

  摘要：

  The electron-rich isomeric complexes CpMo(eta(3)-C3H5)(eta(4)-C4H6) (1a, prone-C3H5; supine-C4H6; 1b, supine-C3H5; supine-C4H6; 1c, supine-C3H5; s-trans-C4H6) do not react with neutral ligands under mild conditions. They are, however, easily protonated by a variety of different acids. Protonation of 1a and 1b involves attack at the terminal position of the allyl ligand and elimination of propene. Protonations with acetic acid show rates in the order 1a > 1b and afford the same product, CpMo(O2CCH3)(eta(4)-C4H6), 2, which can be oxidized to the 17-electron cation [2](+). HBF4 protonation of 1a in the absence of trapping donor molecules affords [CpMo(eta(4)-supine-C4H6)(mu-F2BF2)](n), 3. The latter readily reacts with donor molecules to afford [CpMo(eta(4)-supine-C4H6)L-2][BF4] products (L = MeCN, 4; (BuNC)-N-t, 5; or L-2 = 1,3-butadiene, 6), which are also directly and selectively obtained by protonation of 1a in the presence of the appropriate ligand. Compound 6 has a (supine-C4H6)(s-trans-C4H6) configuration and converts into compound 4 when dissolved in MeCN. Protonation of 1c is much slower relative to the isomers 1a and 1b. The observed products depend on the nature of the solvent. Protonation by HBF4 . Et2O in MeCN affords unstable [CpMo(supine-eta-C3H5)(syn-CH3-prone-eta-C3H4)(NCCH3)][BF4] (7), which rapidly exchanges the MeCN ligand. Decomposition of the latter involves a regioselective reductive coupling of the two allyl ligands to generate 3-methyl-1,5-hexadiene quantitatively. In C6D6, the HBF4 protonation of 1c produces small amounts of propene and a violet precipitate which gives a mixture of 4 and 7 upon treatment in MeCN. In the presence of 1,3-butadiene, protonation of 1c in THF followed by extraction into acetone affords a mixture of 6 and [CpMo(eta-C3H4-CH2CH2-eta-C3H4)(Me2CO)][BF4] (8). Compound 8 converts into [CpMo(eta-C3H4-CH2CH2-eta-C3H4)(L)][BF4] (L = MeCN, 9; PMe3, 10) when treated with the appropriate L. Protonation of 1c in MeCN in the presence of butadiene affords 7 which slowly decomposes, under these conditions, to a mixture of 4 and [CpMo(eta(4)-s-trans-C4H6)(MeCN)(2)](+), 11. The collective results for the protonation of 1c indicate that the proton attacks the s-trans diene ligand in MeCN. The preferred position of attack in nonpolar solvents, on the other hand, is the allyl. The difference of electronic distribution for isomers 1a-c has been investigated by DFT methods. The calculations indicate that the allyl ligand is a stronger donor in the supine configuration, while the diene ligand is both a weaker donor and a weaker acceptor when it is coordinated in the s-trans mode.

  DOI：

  10.1021/ja972587w

文献信息

• Cyclopentadienylmolybdenum(II) and -(III) Complexes Containing Diene and Allyl Ligands. 3. Reactivity Studies of the Bis(butadiene) Complex [CpMo(<i>s-cis-supine</i>-η-C₄H₆)(<i>s-trans</i>-η-C₄H₆)][BF₄]
  作者：Li-Sheng Wang、James C. Fettinger、Rinaldo Poli、Rita Meunier-Prest

  DOI：10.1021/om971079s

  日期：1998.6.1

  s-trans-C4H6)]BF4 (2) reacts with a variety of nucleophilic reagents to afford either substitution of the s-trans-butadiene ligand or regioselective nucleophilic addition to the endo terminal carbon of the s-trans butadiene ligand. The reaction with tBuNC affords the substitution product [CpMo(s-cis-supine-C4H6)(tBuNC)2]BF4 (3). Nucleophilic addition of PMe3 leads to [CpMo(s-cis-supine-C4H6)(syn-p

  化合物[CPMo（s-顺式-仰卧-C 4 H 6）（s-反式-C 4 H 6）] BF 4（2）与多种亲核试剂反应，以取代s-反式-丁二烯s-反式丁二烯配体的内末端碳的配体或区域选择性亲核加成。与t BuNC的反应提供了取代产物[CPMo（s-顺式-仰卧-C 4 H 6）（t BuNC）2 ] BF 4（3）。亲核加成PME的3所导致[合物CPMo（S-顺式仰卧-C 4 ħ 6）（顺式多发-C 3 ħ 4 -1-CH 2 PME 3）] BF 4（4），其已被表征也通过X射线晶体学。甲基锂或烯丙基溴化镁的亲核加成得到[CPMo（s-顺式-仰卧-C 4 H 6）（顺-旋-C 3 H 4 -1-CH 2 R）] BF 4（R = Me，（5）， CH2 CH CH 2（6））。然而，格氏反应还提供了取代产物CPMo（s-顺式-仰卧-C 4 H 6）（倾向-C 3 H 5）。化合物5被二茂铁氧化为[
• Cyclopentadienylmolybdenum(II) and -(III) complexes containing diene and allyl ligands. Part 4. Reactivity studies of the bisallyl complex CpMo(supine-η-C3H5)2 and the allyl-butadiene complex [CpMo(supine-η-C3H5)(supine-η-C4H6)] [PF6] .
  作者：Rinaldo Poli、Li-Sheng Wang

  DOI：10.1016/s0277-5387(98)00164-8

  日期：1998.10

  of [1c] + with methyllithium affords two products, the major one (1c) corresponding to the one-electron reduction pathway and the minor one (CpMo( η 3 -C 3 H 5 )( η 3 -C 3 H 4 -1-Et), 6, ca. 4%) corresponding to nucleophilic addition. Protonation of the 1c:6 mixture affords a 2:1 mixture of cis and trans 2-pentene, in addition to propene. The room temperature Cp 2 Fe + PF 6 − oxidation of 3 in MeCN induces

  摘要由CpMoCl 4和四当量的烯丙基溴化镁合成了化合物CpMo（η3 -C 3 H 5）2，3。尽管该化合物在室温下在供体溶剂中稳定，但在回流的MeCN中加热会通过金属介导的烯丙基-烯丙基偶联过程诱导1,5-己二烯的形成。在室温下用But NC处理3得到CpMo（η3 -C 3 H 5）（Bu t NC）2，4。[CpMo（η3 -C 3 H 5）的类似还原反应是烯丙基自由基的损失。 ）（η4 -C 4 H 6）] +，[1c] +，得到[CpMo（η4 -C 4 H 6）（Bu t NC）2] +，5。用甲基锂处理[1c] +提供两种产物，主要产物（1c）对应于单电子还原途径，次要产物（CpMo（η3 -C 3 H 5）（η3 -C 3 H 4 -1-Et），6，ca 4％）对应于亲核加成。1c的质子化：6混合物除丙烯外，还提供顺式和反式2-戊烯的2：1混合物。室温的Cp 2 Fe +