cis-[MoO2(OSiPh3)2(5,5'-dimethyl-2,2'-bipyridine)] | 245369-61-3

• 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: cis-[MoO2(OSiPh3)2(5,5'-dimethyl-2,2'-bipyridine)]
• CAS: 245369-61-3
• 化学式: C₄₈H₄₂MoN₂O₄Si₂
• 分子量: 862.983
• InChiKey: LIOHBNXRKRFRQH-UHFFFAOYSA-N

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

• 作为产物：
  描述：

  5 5'-二甲基-2,2'-二吡啶 、 [MoO2(OSiPh3)2] 以 二氯甲烷 为溶剂， 以76%的产率得到cis-[MoO2(OSiPh3)2(5,5'-dimethyl-2,2'-bipyridine)]
  参考文献：
  名称：

  The Unperturbed Oxo−Sulfido Functional Group cis-Mo^VIOS Related to That in the Xanthine Oxidase Family of Molybdoenzymes:  Synthesis, Structural Characterization, and Reactivity Aspects

  摘要：

  The oxo-sulfido functional group Cis-(MoOS)-O-VI is essential to the activity of the xanthine oxidase family of enzymes but has proven elusive to synthesis in molecules containing no other four-electron ligands. A direct route to molecules containing this group has been achieved. The reaction system [MoO2(OSiPh3)(2)]/L in dichloromethane yields the complexes [(MoO2)-O-VI(OSiPh3)(2)L] (L = phen (1), Me(4)phen (2), 4,4'-Me(2)bpy (3), 5,5'-Me(2)bpy (4), 2 py (5)) (74-96%), which are shown to have a distorted octahedral structure of crystallographically imposed C-2 symmetry (1, 5) with cis oxo and trans silyloxy ligands. The related reaction system [MoO3S](2-)/2Ph(3)SiCl/L in acetonitrile affords the complexes [(MoOS)-O-VI(OSiPh3)(2)L] (L = phen (6), Me(4)phen (7), 4,4'-Me(2)bpy (8), 5,5'-Me(2)bpy (9)) (36-69%). From the collective results of elemental analysis, mass spectrometry, H-1 NMR, and X-ray structure determinations (6, 7), complexes 6-9 are shown to contain the cis-(MoOS)-O-VI group in molecules with the same overall stereochemistry as dioxo complexes 1-5. The crystal structures of 6 and 7 exhibit O/S disorder, which was modeled in refinements with 50% site occupancies. The Mo=O (1.607(5) (6), 1.645(5) (7) Angstrom) and Mo=S (2.257(3) (6), 2.203(2) (7) Angstrom) bond distances obtained in this way are somewhat shorter and longer, respectively, than expected. Distances obtained 6-9 (Mo=O 1.71-1.72 Angstrom; Mo=S 2.18-2.19 Angstrom) are considered more satisfactory and are in good agreement with EXAFS values for xanthine oxidase. Molybdenum K-edge data for 1 and 6-9 are reported. Reaction of 7 with Ph3P in dichloromethane results in sulfur abstraction and formation of [(MoOCl)-O-V(OSiPh3)(2)(Me(4)phen)] (10), which has a distorted octahedral structure with cis O/Cl and cis silyloxy ligands. Sulfur rather than oxygen abstraction is favored by relative Mo=O/Mo=S bond strengths. Complexes 6-9 should allow exploration of the biologically significant Cis-(MoOS)-O-VI group.

  DOI：

  10.1021/ic990440v