trans-Mo2(DAniF)2(OOCCH3)2 | 679398-07-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans-Mo2(DAniF)2(OOCCH3)2
• 英文别名: trans-Mo2(μ-N,N′-bis(4-methoxyphenyl)formamidinato-κ2N:N′)2(OOCCH3)2；trans-Mo2(N,N'-di-p-anisylformamidinato)2(acetato)2；trans-Mo2(DAniF)2(acetato)2；cis-Mo2(N,N'-di(p-anisyl)formamidinate)2(acetate)2；trans-[Mo2(DAniF)2(OAc)2]；(4-methoxyphenyl)-[(4-methoxyphenyl)iminomethyl]azanide;molybdenum(2+);diacetate
• CAS: 679398-07-3
• 化学式: C₃₄H₃₆Mo₂N₄O₈
• 分子量: 820.562
• InChiKey: KUOABPTZSYATFY-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  5.65
• 重原子数：
  48
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  144
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  trans-Mo2(DAniF)2(OOCCH3)2 、 1,5,7-三氮杂双环[4.4.0]癸-5-烯 在 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 5.0h， 以83%的产率得到
  参考文献：
  名称：

  胍基配体通过系统性取代对二氧化钼系统的氧化还原电位的调节。

  摘要：

  我们报告了一系列Mo2（DAniF）4-n（hpp）n（n = 1-3）类型的二钼桨轮配合物的合成和表征，其中DAniF是N，N'-di-p-的阴离子茴香基-甲am和hpp是1,3,4,6,7,8-六氢-2H-嘧啶[1,2-a]嘧啶的阴离子。在用更碱性的胍盐系统地取代甲酰胺盐配体后，研究了这些四方桨轮二钼化合物对电子结构的影响。钼酸根配体取代后，桨叶结构中的Mo-Mo距离减小，发现Mo2（DAniF）3（hpp）（1）和trans-Mo2（DAniF）2（分别为2.0844（6）和2.0784（6）。 hpp）2（2）。电化学研究表明，Mo25 + / Mo24 +对的半波电势在辅助配体取代范围为-0时发生阴极移位。四甲酰胺酸复合物的电压为286 V，四胍基类似物的电压为-1.795 V，1、2和3（Mo2（DAniF）（hpp）3）的氧化还原电位分别为-0.75，-1.07和-1.14V

  DOI：

  10.1021/acs.inorgchem.9b03394
• 作为产物：
  描述：

  乙酸钼(II)二聚体 、 N,N'-bis(4-methoxyphenyl)iminoformamide 在 sodium methylate 作用下， 以 四氢呋喃 为溶剂， 生成 trans-Mo2(DAniF)2(OOCCH3)2
  参考文献：
  名称：

  胍基配体通过系统性取代对二氧化钼系统的氧化还原电位的调节。

  摘要：

  我们报告了一系列Mo2（DAniF）4-n（hpp）n（n = 1-3）类型的二钼桨轮配合物的合成和表征，其中DAniF是N，N'-di-p-的阴离子茴香基-甲am和hpp是1,3,4,6,7,8-六氢-2H-嘧啶[1,2-a]嘧啶的阴离子。在用更碱性的胍盐系统地取代甲酰胺盐配体后，研究了这些四方桨轮二钼化合物对电子结构的影响。钼酸根配体取代后，桨叶结构中的Mo-Mo距离减小，发现Mo2（DAniF）3（hpp）（1）和trans-Mo2（DAniF）2（分别为2.0844（6）和2.0784（6）。 hpp）2（2）。电化学研究表明，Mo25 + / Mo24 +对的半波电势在辅助配体取代范围为-0时发生阴极移位。四甲酰胺酸复合物的电压为286 V，四胍基类似物的电压为-1.795 V，1、2和3（Mo2（DAniF）（hpp）3）的氧化还原电位分别为-0.75，-1.07和-1.14V

  DOI：

  10.1021/acs.inorgchem.9b03394
• 作为试剂：
  描述：

  三氯乙酸乙酯 在 trans-Mo2(DAniF)2(OOCCH3)2 、 1-甲基-3,6-双(三甲基硅基)环己-1,4-二烯 、 四丁基氯化铵 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以62%的产率得到二氯乙酸乙酯
  参考文献：
  名称：

  Mixed-ligand complexes of paddlewheel dinuclear molybdenum as hydrodehalogenation catalysts for polyhaloalkanes

  摘要：

  一种混合配体的二钼络合物 Mo₂(OAc)₂[CH(NAr)₂]₂，与1-甲基-3,6-双(三甲基硅基)-1,4-环己二烯和nBu₄NCl 结合，展现出对脱卤反应具有高催化活性。

  DOI：

  10.1039/c5sc00721f

文献信息

• Strong Electronic Interaction between Two Dimolybdenum Units Linked by a Tetraazatetracene
  作者：F. Albert Cotton、Zhong Li、Chun Y. Liu、Carlos A. Murillo、Dino Villagrán

  DOI：10.1021/ic051614d

  日期：2006.1.1

  X-ray crystallography and, as appropriate, by various techniques such as NMR, EPR, near-IR, and UV-vis. The fluoflavinate ligand strongly mediates electronic communication between the dimetal units, and the mixed valence species 2 can be described as electronically delocalized. Calculations at the DFT level using a variety of functionals support such an assignment and indicate that a strong transition

  大型刚性二价氟黄素，C（14）H（8）N（4）（2）（-），由四个稠合且平面的六元环与四个氮供体原子组成，已用于将两种金属连接至-金属键合和具有氧化还原活性的Mo（2）（n）（）（+）单元，每个单元都由三个附加基团局部桥接，统称为[Mo（2）]。在1中，[Mo（2）]单元是Mo（2）（DAniF）（3）（DAniF = N，N'-di-p-茴香基甲酰胺基），在5中，它们是反式Mo（2）（ DAniF）（2）（O（2）CCH（3））组。这些[Mo（2）]（氟黄酸酯）[Mo（2）]化合物显示三个可逆的单电子氧化步骤，比迄今已知的所有其他[Mo（2）]（连接基）[Mo（2）]种类多一个。前两个氧化还原过程是基于金属的，与仅包含一个带有单阴离子氟黄素配体的二钼单元的明轮化合物4相比，第三个被指定为配体氧化。1的化学氧化分别产生单氧化和双氧化的物质2和3。所有化合物均已通过X射线晶体学表征，并在适当
• Synthesis, X-ray Structure Analysis and Spectroscopic Characterization of trans-Aquabis(µ-benzoato-κ2 O:O′) bis[µ-N,N′-bis(4-methoxyphenyl) formamidinato-κ2 N:N′] dimolybdenum(II)
  作者：Ya-Jie Kong、Li-Juan Han

  DOI：10.1007/s10870-017-0698-7

  日期：2017.12

  phenyl rings of 3.44 Å and the center-to-center distance of 3.83 Å. The coordinated water oxygen atoms act as donors and uncoordinated methoxyl group oxygen atoms act as acceptors in intermolecular O–H⋯O hydrogen bonds. π–π stacking between phenyl rings assemble the molecules into a three-dimensional framework.Graphical AbstractThe offset π–π stacking between phenyl rings of quadruply bonded Mo24+ paddle-wheel

  摘要标题化合物 trans-Mo2(DAniF)2(OOCC6H5)2(H2O) (I) 有一个四重键合的 Mo24+ 单元，由两个 N,N'-双（4-甲氧基苯基）甲脒（称为 DAniF）配体和两个苯甲酸酯 (OOCC6H5) 基团横向和轴向由一个水族氧原子配位。该化合物在空间群 C2/c 中结晶，在不对称单元中有一个分子，并且具有 2.0983(4) Å 的 Mo-Mo 键长，这是二钼四键的典型特征。在晶体中，苯环对之间的偏移 π-π 堆积形成一维线性链，垂直于 Mo-Mo 方向，苯环之间的距离为 3.44 Å，中心到中心的距离为 3.83 Å . 配位的水氧原子作为供体，未配位的甲氧基氧原子作为分子间 O-H⋯O 氢键的受体。苯环之间的π-π堆积将分子组装成一个三维框架。图形摘要四重键合的Mo24+桨轮分子的苯环之间的偏移π-π堆积形成一维线性链。
• Supramolecular assemblies of dimolybdenum transoids built by Mo2-enhanced perfluorophenyl-perfluorophenyl synthons
  作者：Li Juan Han、Li Yan Fan、Miao Meng、Xuefeng Wang、Chun Y. Liu

  DOI：10.1039/c1dt11490e

  日期：——

  Two supramolecular assemblies were developed by the dimmolybdenum paddlewheel complex trans-Mo2(DAniF)2(O2CC6F5)2 (1) (ancillary ligand DAniF = N,N′-di-(p-anisyl)formamidinate) through intermolecular offset face to face C6F5⋯C6F5 interactions. The two networks are different because of the presence and absence of tetrahydrofuran (THF) axial coordination to the Mo2 units, but feature commonly short interplanar distances between the two paired perfluorophenyl groups, that is, 3.30 Å and 3.23 Å, respectively, which are similar to the shortest intermolecular C⋯F contacts between two atoms in meta and ortho positions. Consistently, as indicated by the Mulliken population analysis, the dipole moments for the meta and ortho C–F bonds are considerably enlarged because the pentafluorobenzoate groups are bonded to the dimetal unit. In comparison, X-ray structural and theoretical analyses were also made for the parent molecule pentafluorobenzoic acid. The resultant data show that charge distribution on the perfluorophenyl group has a major influence on the C6F5⋯C6F5 binding mode. Therefore, it is evidenced that the dimetal unit plays a role in further polarizing the highly polarized C–F bonds and the intermolecular perfluorophenyl-perfluorophenyl interactions are dominated by the C⋯F dipole–dipole interaction, rather than aromatic-aromatic π–π stacking.

  通过分子间偏移面对面C6F5⋯ 相互作用，二茂钼桨状复合物反式Mo2(DAniF)2(O2C )2 (1)（辅助配体DAniF = N,N′-二-(对-茴香基)甲脒）形成了两个超分子组装。由于Mo2单元存在或不存在四氢呋喃（THF）轴向配位，这两个网络是不同的，但两个配对的全氟苯基基团之间的平面间距通常很短，分别为3.30 Å和3.23 Å，与两个原子在间位和邻位之间的最短分子间C⋯F接触相似。正如穆利肯（Mulliken）人口分析所示，由于五
• Dimolybdenum-Containing Molecular Triangles and Squares with Diamidate Linkers:  Structural Diversity and Complexity
  作者：F. Albert Cotton、Chun Y. Liu、Carlos A. Murillo、Xiaoping Wang

  DOI：10.1021/ic0521473

  日期：2006.3.1

  By employing cis-Mo-2(DAniF)(2)(2+) (DAniF = N,N'-di(p-anisyl)formamidinate) as the vertex building block and terephthaloyldiamidate as the linker, four dimolybdenum-containing cyclic oligomers have been synthesized and structurally characterized. In these compounds, described by the general formula [CiS-Mo-2(DAniF)(2)((ArNOC)(2)C6H4)(2)](n), n = 3 and 4, the geometry and composition of the products are affected by the identity of the aromatic groups of the linker. When Ar = phenyl, n = 3 (1a and 1b); however, n = 4 for Ar = p-trifluoromethylphenyl (2) and when Ar = m-trifluoromethylphenyl (3). All these compounds have a central cavity, shaped by the diamidate linker, that is capable of serving as host to guest molecules in a selective manner. For compounds 2 and 3, self-assembly that takes place in the crystalline state entails intermolecular C-(HF)-F-...-C interactions. Such interactions generate a one-dimensional network with a tunnel cross section of 10 x 10 angstrom(2) in 2, whereas in 3, they result in a cage in which two THF molecules are encapsulated. The (FH)-H-... distances vary in a broad range from 2.38 to 2.70 angstrom.
• Systematic Preparation of Mo₂⁴⁺ Building Blocks for Supramolecular Assemblies
  作者：F. Albert Cotton、Chun Y. Liu、Carlos A. Murillo

  DOI：10.1021/ic035433s

  日期：2004.4.1

  The preparation of additional and useful building blocks for the construction of supramolecular entities with quadruply bonded Mo-2(4+) units has been explored, and five new mixed-ligand complexes with three types of ligands and various basicities are reported. The ligands used were the DAniF (N,N'-di-p-anisylformamidinate) anion, the acetate anion, and neutral acetonitrile molecules. The formamidinate ligands are the least labile, and the acetonitrile molecules are the most labile. This difference as well as a relatively strong trans directing influence by the formamidinate anions in ligand substitution reactions allows designed synthesis of various mixed-ligand building blocks, including rare pairs of cis and trans isomers. The new compounds are cis-Mo-2(DAniF)(2)(O2CCH3)(2) (1), trans-Mo-2(DAniF)(2)-(O2CCH3)(2) (2), trans-[Mo-2(DAniF)(2)(O2CCH3)(CH3CNeq)(2)]BF4 (3), trans-[Mo-2(DAniF)(2)(CH3CNeq)(4)] (BF4)(2) (4), and [Mo-2(O2CH3)(CH3CNeq)(6)(CH3CNax)](BF4)(3) (5), where eq and ax designate equatorial and axial ligands, respectively. A comparison with some previously synthesized complexes is given along with a discussion of the overall reactivity of all compounds.