[n-Bu4N][(η5-C5Me5)MoO3] | 142188-62-3

• 英文名称: [n-Bu4N][(η5-C5Me5)MoO3]
• 英文别名: tetra-n-butylammonium {trioxo(η5-pentamethylcyclopentadienyl)molybdate(VI)}；[n-Bu₄N][(η⁵-C₅Me₅)MoO₃]；[nBu₄N](η⁵-C₅Me₅MoO₃)；[nBu₄N](Cp*MoO₃)；[NBu4]((η5-C5Me5)MoO3)；[(n-C4H9)4N][(C5Me5)MoO3]；[Bu4N][Cp(*)MoO3]
• CAS: 142188-62-3
• 化学式: C₁₀H₁₅MoO₃*C₁₆H₃₆N
• 分子量: 521.636
• InChiKey: HEZVUXHBNQUMLS-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：

  [n-Bu4N][(η5-C5Me5)MoO3] 、 以 甲醇 为溶剂， 以40%的产率得到
  参考文献：
  名称：

  Proust, Anna; Thouvenot, Rene; Herson, Patrick, Journal of the Chemical Society, Dalton Transactions, 1999, # 1, p. 51 - 56

  摘要：

  DOI：
• 作为产物：
  描述：

  tetra-n-butylammonium hydroxide 、 tetraoxo-μ-oxobis(pentamethylcyclopentadienyl)dimolybdenum(VI) 以 四氢呋喃 、 水 为溶剂， 以71%的产率得到[n-Bu4N][(η5-C5Me5)MoO3]
  参考文献：
  名称：

  Sundermeyer, Joerg; Radius, Udo; Burschka, Christian, Chemische Berichte, 1992, vol. 125, # 11, p. 2379 - 2384

  摘要：

  DOI：

文献信息

• Heterometallic Cerium(IV) Perrhenate, Permanganate, and Molybdate Complexes Supported by the Imidodiphosphinate Ligand [N(<i>i</i>-Pr₂PO)₂]⁻
  作者：Guo-Cang Wang、Herman H. Y. Sung、Feng-Rong Dai、Wai-Hang Chiu、Wai-Yeung Wong、Ian D. Williams、Wa-Hung Leung

  DOI：10.1021/ic302567e

  日期：2013.3.4

  with [n-Bu4N]2[MoO4], afforded [CeN(i-Pr2PO)2}3]2(μ-MoO4) (4). Reaction of trans-Ce[N(i-Pr2PO)2]2(NO3)2 (5), which was prepared from (NH4)2Ce(NO3)6 and K[N(i-Pr2PO)2], with 2 equiv of [n-Bu4N][Cp*MoO3] yielded trans-Ce[N(i-Pr2PO)2]2(Cp*MoO3)2 (6). 4 can catalyze the oxidation of methyl phenyl sulfide with tert-butyl hydroperoxide with high selectivity. The crystal structures of complexes 3–6 have been

  合成了含亚氨基二次膦酸酯配体[N（i -Pr 2 PO）2 ] -的高金属酸铈（IV），高锰酸盐和钼酸盐络合物，并对其反应性进行了研究。用AgMO 4（M = Re，Mn）处理Ce [N（i -Pr 2 PO）2 ] 3 Cl（1）得到Ce [N（i -Pr 2 PO）2 ] 3（ReO 4）（2）或Ce 2 [N（i -Pr 2 PO）2 ] 6（MnO 4）2（3）。在固态状态下，3由[Ce 2 N（i -Pr 2 PO）2 } 6（MnO 4）] +具有弱Ce-OMn相互作用[Ce-OMn距离= 2.528（8）Å ]的部分组成]和非配位的MnO 4 -抗衡阴离子。而3是在固体状态和乙腈溶液稳定，它在其它有机溶剂，如CH容易分解2氯2。3在室温下可将乙苯氧化为苯乙酮。治疗1用的AgBF 4，随后用反应[ Ñ -Bu 4 N] 2 [的MOO 4 ]，得到[CE N（我-Pr 2 PO）2
• Iron–molybdenum-oxo complexes as initiators for olefin autoxidation with O₂
  作者：Jan P. Falkenhagen、Christian Limberg、Serhiy Demeshko、Sebastian Horn、Michael Haumann、Beatrice Braun、Stefan Mebs

  DOI：10.1039/c3dt52349g

  日期：——

  The reaction between [(TPA)Fe(MeCN)2](OTf)2 and [nBu4N](Cp*MoO3) yields the novel tetranuclear complex [(TPA)Fe(μ-Cp*MoO3)]2(OTf)2, 1, with a rectangular [Mo–O–Fe–O–]2 core containing high-spin iron(II) centres. 1 proved to be an efficient initiator/(pre)catalyst for the autoxidation of cis-cyclooctene with O2 to give cyclooctene epoxide. To test, which features of 1 are essential in this regard, analogues with zinc(II) and cobalt(II) central atoms, namely [(TPA)Zn(Cp*MoO3)](OTf), 3, and [(TPA)Co(Cp*MoO3)](OTf), 4, were prepared, which proved to be inactive. The precursor compounds of 1, [(TPA)Fe(MeCN)2](OTf)2 and [nBu4N](Cp*MoO3) as well as Cp2*Mo2O5, were found to be inactive, too. Reactivity studies in the absence of cyclooctene revealed that 1 reacts both with O2 and PhIO via loss of the Cp* ligands to give the triflate salt 2 of the known cation [((TPA)Fe)2(μ-O)(μ-MoO4)]2+. The cobalt analogue 4 reacts with O2 in a different way yielding [((TPA)Co)2(μ-Mo2O8)](OTf)2, 5, featuring a Mo2O84− structural unit which is novel in coordination chemistry. The compound [(TPA)Fe(μ-MoO4)]2, 6, being related to 1, but lacking Cp* ligands failed to trigger autoxidation of cyclooctene. However, initiation of autoxidation by Cp* radicals was excluded via experiments including thermal dissociation of Cp2*.

  [(TPA)Fe(MeCN)2](OTf)2与[nBu4N](Cp*MoO3)反应生成了新型四核复合物[(TPA)Fe(δ-Cp*MoO3)]2(OTf)2，即 1，其矩形[MoâOâFeâOâ]2 内核含有高自旋铁（II）中心。事实证明，1 是顺式环辛烯与 O2 自氧化生成环辛烯环氧化物的高效引发剂/（预）催化剂。为了测试 1 在这方面的基本特征，我们制备了具有锌（II）和钴（II）中心原子的类似物，即[(TPA)Zn(Cp*MoO3)](OTf), 3 和[(TPA)Co(Cp*MoO3)](OTf), 4，事实证明它们没有活性。发现 1 的前体化合物 [(TPA)Fe(MeCN)2](OTf)2 和 [nBu4N](Cp*MoO3) 以及 Cp2*Mo2O5 也没有活性。在没有环辛烯的情况下进行的反应研究表明，1 通过失去 Cp* 配体与 O2 和 PhIO 反应，生成已知阳离子[((TPA)Fe)2(δ-O)(δ-MoO4)]2+ 的三盐酸盐 2。钴类似物 4 与 O2 以不同的方式发生反应，生成[((TPA)Co)2(δ-Mo2O8)](OTf)2, 5，其特点是具有配位化学中新颖的 Mo2O84â 结构单元。化合物[(TPA)Fe(δ- )]2, 6 与 1 有关，但缺少 Cp* 配体，未能引发环辛烯的自氧化反应。不过，通过包括 Cp2* 热解离在内的实验，排除了 Cp* 自由基引发自氧化的可能性。
• Molecular Compounds with Mo-O-Bi Moieties
  作者：Stefan Roggan、Christian Limberg、Burkhard Ziemer

  DOI：10.1002/anie.200500375

  日期：2005.8.19
• Reactivity and Properties of [−O−Bi^III...OMo−]<i>_n</i> Chains
  作者：Stefan Roggan、Christian Limberg、Burkhard Ziemer、Maike Siemons、Ulrich Simon

  DOI：10.1021/ic061198c

  日期：2006.10.30

  A coordination polymer [Cp*(O)(2)Mo-O-Bi(o-tolyl)(2)](n1) II, containing Mo-O-Bi and Mo=O center dot center dot center dot Bi moieties was investigated with respect to its behavior in contact with OH- and Cp2MoH2 and as potential single source precursor in the polyol method. It turned out that hydroxide as a base breaks up the polymer to yield Cp*MoO3- and (o-tolyl) 2BiOH. The latter polymerizes to give the coordination polymer [(o-tolyl)(2)BiOH](n1) 1. Alternatively, 1 can be prepared by reacting [(o-tolyl)(2)Bi(hmpa)(2)]SO3CF3 with NBu4OH/H2O in thf/water. If, however, NBu4OH/MeOH is used in dichloromethane as the solvent, the (o-tolyl)(2)BiOH formed intermediately undergoes methanolysis, and finally, [(o-tolyl)(2)BiOMe](n1) 3, is isolated. Although 1 and 3 are very similar compounds, their crystal structures differ significantly: while the structure of 1 is dominated by secondary bonding leading to seesaw-type coordination geometries around the Bi centers, the Bi atoms in 3 are coordinated in a distorted tetrahedral fashion, and secondary bonding plays only a minor role. If 1 is dissolved in a nonpolar, nonprotic solvent, condensation reactions occur immediately leading to [(o-tolyl)(2)BiOBi(o-tolyl)(2)], 2, which can be obtained on a preparative scale this way. Compound 3 which can be prepared in good yields may prove to be a useful starting material in bismuth chemistry. Here, it was shown to react with molybdocene dihydrides to provide stable Bi-substituted molybdocene monohydrides [Cp-R(2)-Mo( H)(Bi(o-tolyl)(2))] (R = Me 4, R = H 5); compounds of that type were identified in solution before but had so far eluded isolation. Compound 4, whose crystal structure is discussed, also forms when II is treated with methylated molybdocene dihydride. This obviously leads to the formation of Mo-Bi bonds (-> 4), as well as Mo-OH units, which undergo condensation reactions leading to Mo-O-Mo moieties (i.e., [Cp*2Mo2O5] is formed as a byproduct). The use of II as precursor in the polyol method successfully led to bismuthmolybdate nanoparticles (accompanied by crystallites); however, no single phase is obtained, but biphasic materials consisting of Bi2Mo2O9 and Bi2MoO6, whose ratio can be determined by the choice of the hydrolyzing reagent, are formed instead. One of these materials proved to be capable of sensing EtOH selectively at elevated temperatures.
• Reactivity of Organometallic Molybdate toward Lanthanide Cations. Synthesis and Structure of Polynuclear Lanthanide−Molybdate Complexes
  作者：M. Hashimoto、M. Takata、A. Yagasaki

  DOI：10.1021/ic991221c

  日期：2000.8.1

  Novel polynuclear rare earth compounds [La-3(OH2)(7)-(Cp*MoO3)(2)(NO3)(7)] and [La-3(OH2)(5)(THF)(Cp*MoO3)(2)-(NO3)(6)](2)(NO3)(2) were synthesized by reacting [(n-C4H9)(4)N][CP*MoO3] With La(NO3)(3). 6H(2)O in THF. X-ray crystal structural analyses revealed that both these compounds are composed of a La3Mo2O6 unit in which the metal atoms arrange themselves into a trigonal bipyramid. The Ce analogues were also obtained.[GRAPHICS]