| 147513-97-1

• CAS: 147513-97-1
• 化学式: C₂₆H₂₄MoN₂O₁₀
• 分子量: 620.424
• InChiKey: YWPUGDQEQXXCKT-CMMKKUAHSA-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

• 作为产物：
  描述：

  钼,四羰基(1,10-亚铁试剂(邻二氮杂菲)-kN1,kN10)-,(OC-6-22)- 、 马来酸二甲酯 以 甲苯 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  八面体双（马来酸酯）钼（0）配合物的合成，结构和异构

  摘要：

  Treatment Of MO(CO)3(CH3CN)3 in acetonitrile with 1 equiv of o-phenylenediamine (PDA) and excess dimethyl maleate (DMMA) at ambient temperature gave trans-Mo(CO)2(DMMA)2-(PDA) (1). There are three possible conformations d-I-d-III for the two trans DMMA ligands in 1. On the basis of the chemical shifts of olefin and methyl protons, the conformation of the DMMA ligands in 1 was determined to be d-I. Complexes trans-MO(CO)2(DMMA)2(NN) (NN = bpy (2), phen (3)) were synthesized by treating MO(CO)4(NN) with excess DMMA in refluxing toluene for 4 h. The conformation of these complexes in solution indicated by NMR data is d-III. Complexes 1-3 isomerize to the corresponding trans-MO(CO)2(DMMA)(DMFU)(NN) (NN = PDA (4), bpy (5), phen (6)) and then to trans-MO(CO)2(DMFU)2(NN). There are four possible conformations e-I-e-IV of a trans-MO(CO)2(DMMA)(DMFU)(NN) complex. The conformation of Mo(CO)2(DMMA)(DMFU)(PDA) (4) determined by X-ray crystallography was shown to be e-1. The same conformation was also observed in solution by NMR spectroscopy. Compound 4 crystallizes in monoclinic space group P2(1)/c with cell parameters a = 14.636(3) angstrom, b = 9.998(3) angstrom, c = 15.845(6) angstrom, beta = 93.02(1)-degrees, and Z = 4; R = 0.0309 and R(w) = 0.0295 for 2552 independent reflections with intensity greater-than-or-equal-to 3sigma(I). The low-temperature H-1 NMR spectra of 5 and 6 show that they exist as mixtures of rotamers e-II and e-Ill that undergo exchange at ambient temperature. The mechanism for the isomerization of coordinated DMMA to DMFU ligand is discussed.

  DOI：

  10.1021/om00033a011

文献信息

• Synthesis, structure, and properties of octahedral d6 bis(alkene) complexes of molybdenum
  作者：Chen Hsing Lai、Chien Hong Cheng、Wen Ch'ing Chou、Sue Lein Wang

  DOI：10.1021/om00028a027

  日期：1993.4

  Mo(CO)3(CH3CN)(NN) obtained by treating Mo(CO)3(CH3CN)3 with 1 equiv of bidentate nitrogen ligand (NN) reacts with excess DMFU (dimethyl fumarate) to give MO(CO)2(NN)-(DMFU)2 (NN = o-phenylenediamine (1), en (2), phen (3), and bpy (4)). These products are mixtures of diastereomers a and b which resulted from face selection of the two DMFU ligands for coordination to the metal center. The two diastereomers 1a and 1b of 1 were separated by column chromatography. The structure of compound la determined by X-ray crystallography is distorted octahedral with the two DMFU ligands being trans to each other and cis to CO and PDA ligands. The two alkenes are mutually orthogonal and each eclipses a N-M-C vector. In addition, they are bound to the Mo center in a fashion with all four ester groups lying between the carbonyl and the amino groups. The absolute configuration of the olefin carbons of the DMFU ligands in la is RRRR or SSSS. The geometry of lb is similar to that of la except that different faces of the DMFU ligands (RRSS or SSRR) are coordinated to the Mo center. As a result, the four ester groups and four olefin protons are equally distributed in the four regions defined by the two intersected N-Mo-CO vectors. For product 2, only one diastereomer having structure a was observed. Due to internal hydrogen bonding between the amino protons and the keto groups on the DMFU ligands, which restricts the rotation of the coordinated DMFU, 1a, 1b, and 2a are all static in solution at ambient temperature. Similar to product 1, both products 3 and 4 also are mixtures of diastereomers a and b. As indicated by the low-temperature H-1 NMR spectra, 3a and 4a consist of rotational isomers I and II which undergo rapid mutual exchange at ambient temperature. 3b and 4b exhibit fluxional behavior on the NMR time scale due to rotation of the DMFU ligands. The structure of 3b was also determined from X-ray diffraction measurements. The results confirm the general structural features concluded from NMR data of these species. la crystallizes in monoclinic space group C2/c with unit cell parameters a = 12.311(3) angstrom, b = 11.027(3) angstrom, c = 17.000(6) angstrom, beta = 99.32(2)-degrees, and D(c) = 1.599 g cm-3 for Z = 4; least-squares refinement based on 2018 independent observed reflections produced a final R value 0.028. Compound 3b belongs to triclinic space group P1BAR with unit cell parameters a = 9.546(2) angstrom, b = 10.072(2) angstrom, c = 14.886(3) angstrom, beta = 77.76(1)-degrees-, and D(c) = 1.537 g cm-3 for Z = 2; after refinement, the final R value was 0.034 on the basis of 4727 independent observed reflections.