[(cyclopentadienyl)2(μ-SCH3)3(acetonitrile)2dimolybdenum(III)] | 185040-57-7

• 英文名称: [(cyclopentadienyl)2(μ-SCH3)3(acetonitrile)2dimolybdenum(III)]
• 英文别名: [Mo2Cp2(μ-SMe)3(acetonitrile)2](1+)；[Mo2Cp2(μ-SCH3)3(CH3CN)2](1+)
• CAS: 185040-57-7
• 化学式: C₁₇H₂₅Mo₂N₂S₃
• 分子量: 545.477
• InChiKey: IBVJCKCUIBBEOD-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(cyclopentadienyl)2(μ-SCH3)3(acetonitrile)2dimolybdenum(III)] 、 四丁基亚硝酸铵 在 NaBH₄ 作用下， 以 四氢呋喃 为溶剂， 生成 [Mo2Cp2(μ-SCH3)3(μ-η1,η1-acetamidato)]
  参考文献：
  名称：

  Nitrate‐ and Nitrite‐Assisted Conversion of an Acetonitrile Ligand Into an Amidato Bridge at an {Mo ₂ (Cp) ₂ (μ‐SMe) ₃ } Core: Electrochemistry of the Amidato Complex [Mo ₂ (Cp) ₂ (μ‐SMe) ₃ {μ‐η ¹ ,η ¹ ‐OC(Me)NH}] ⁺

  摘要：

  AbstractTreatment of [Mo2(Cp)2(μ‐SMe)3(MeCN)2]+ (1+) with NO3– or NO2– results in the conversion of one terminally bound acetonitrile ligand into an amidato bridge. The reaction produces [Mo2(Cp)2(μ‐SMe)3{μ‐η1,η1‐OC(Me)NH}]0/+ (20/+) and involves the formation of an intermediate, which was detected by cyclic voltammetry but which could not be isolated, and which likely arises from the substitution of the NOx anion for one MeCN ligand. The electrochemical behaviour of 2+ was studied by cyclic voltammetry in THF and MeCN. The reduction of 2+ in the presence of acid (HBF4/H2O or HBF4/Et2O) in these solvents leads to the release of the amidate bridge. Controlled‐potential electrolysis of 2+ in MeCN in the presence of acid produces 1+ quantitatively; the charge consumed (>1 F mol–1 of 1+) indicates that electrons are also used to reduce protons. This was confirmed by the formation of 2+ (in variable amounts depending on the conditions) on treating 2 with acid. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  DOI：

  10.1002/ejic.200500315
• 作为产物：
  描述：

  [(cyclopentadienyl)2(μ-SCH3)3(p-toluenesulfonato)(H2O)dimolybdenum(III)] 、 乙腈 以 not given 为溶剂， 生成 [(cyclopentadienyl)2(μ-SCH3)3(acetonitrile)2dimolybdenum(III)]
  参考文献：
  名称：

  Henanf, Marc Le; Roy, Christine Le; Muir, Kenneth W., European Journal of Inorganic Chemistry, 2004, # 8, p. 1687 - 1700

  摘要：

  DOI：

文献信息

• Influence of the initial bonding mode of the hydrocarbyl bridge on the mechanisms and products of the electrochemical reduction of alkyne- and vinylidene dimolybdenum tris(µ-thiolate) complexes
  作者：Alan Le Goff、Christine Le Roy、François Y. Pétillon、Philippe Schollhammer、Jean Talarmin

  DOI：10.1039/b614948k

  日期：——

  acid-free solutions since 1+ reduces in two diffusion-controlled one-electron steps while the first reduction of 3+ is characterized by slow electron transfer kinetics. Controlled-potential reduction of both 1+ and 3+ produces a mixture of the acetylide [Mo2Cp2(μ-SMe)3(μ-η1:η2-CCPh)] (2) and alkylidyne complexes [Mo2Cp2(μ-SMe)3(μ-η1-CCH2Ph)] (4). In the presence of acid, the electrochemical reduction of 1+

  电化学的 减少异构体配合物，[沫2的CP 2（μ-SME）3（μ-η 1：η 1 -HCCPh）] +（1 +）和[沫2的CP 2（μ-SME）3（μ-η 1： η 2 -C CHPh配合]）+（3 +），其中烃基在η桥梁1 η：1 -或η 1：η 2模式中，进行了研究循环伏安法在不存在和存在酸的条件下，在thf- [NBu 4 ] [PF 6 ]和CH 2 Cl 2- [NBu 4 ] [PF 6 ]中进行控制电势电解。CC片段的结合模式在无酸溶液中诱导了复合物的不同电化学行为，因为1 +在两个扩散控制的单电子步骤中还原，而3 +的首次还原具有缓慢的特征。电子转移动力学。控制电位减少二者的1 +和3 +产生的混合物乙炔化物[沫2的CP 2（μ-SME）3（μ-η 1：η 2 -CCPh）]（2）和次烷基络合物[沫2的CP 2（μ-SME）3（μ-η 1个-CCH 2 PH） ]（4）。在酸的存在下，根据ECE方法发生1
• Electrochemical deprotection of a substrate binding site in [Mo₂(cp)₂(µ-SMe)₃(µ-Cl)](cp =η⁵-C₅H₅)via chloride-bridge opening. Kinetics of MeCN and Bu^tNC binding at this site
  作者：Frédéric Barrière、Yves Le Mest、François Y. Pétillon、Sylvie Poder-Guillou、Philippe Schollhammer、Jean Talarmin

  DOI：10.1039/dt9960003967

  日期：——

  The access to a co-ordination site in the quadruply bridged complex [Mo-2(cp)(2)(mu-SMe)(3)(mu-Cl)] (cp = eta(5)-C5H5) has been found to be redox controlled. Electrochemical one-electron oxidation of the complex unlocks the chloride bridge but the radical cation retains the quadruply bridged geometry of the neutral parent as indicated by cyclic voltammetry and EPR spectroscopy. The chloride bridge opens up in the presence of a substrate (Y=Z = MeCN, Bu(t)NC, Me(2)C(6)H(3)NC or CO), leading to the formation of [Mo-2(cp)(2)(mu-SMe)(3)Cl(Y=Z)](.+) derivatives. The site is sensitive to the electronic properties of the substrate, and kinetic studies of the substrate-binding step demonstrated that Bu(t)NC reacts faster and is bound more tightly at [Mo-2(cp)(2)(mu-SMe)(3)Cl](.+) than is MeCN. The reduction of [Mo-2(cp)(2)(mu-SMe)(3)Cl(Y=Z)](.+) is reversible for Y=Z = CO and RNC (R = Bu(t) or C(6)H(3)Me(2)) whereas MeCN is lost on reduction. In this case the fact that the chloride ligand is still present at the neighbouring molybdenum centre allows regeneration of the parent complex via bridge reclosure. The reactivity of [Mo-2(cp)(2)(mu-SMe)(3)(mu-Cl)] in MeCN has also been investigated: instead of the bridge-opening process of the radical cation, the neutral parent loses the chloride bridge in MeCN; the resulting bis(acetonitrile) cation, [Mo-2(cp)(2)(mu-SMe)(3)(MeCN)(2)](+), has been isolated and characterized.