hexacarbonyl[μ-η(4)-(1-methyl-1-(1-pyrrolidiniumylidene)2-butyne)]dicobalt(Co-Co) hexafluorophosphate | 162382-01-6

• 英文名称: hexacarbonyl[μ-η(4)-(1-methyl-1-(1-pyrrolidiniumylidene)2-butyne)]dicobalt(Co-Co) hexafluorophosphate
• CAS: 162382-01-6
• 化学式: C₁₅H₁₄Co₂NO₆*F₆P
• 分子量: 567.23
• InChiKey: HYLLLWATJNHKHS-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：

  hexacarbonyl[μ-η(4)-(1-methyl-1-(1-pyrrolidiniumylidene)2-butyne)]dicobalt(Co-Co) trifluoromathanesulfonate 、 tert-butylammonium hexafluorophosphate(V) 以 二氯甲烷 为溶剂， 以31%的产率得到hexacarbonyl[μ-η(4)-(1-methyl-1-(1-pyrrolidiniumylidene)2-butyne)]dicobalt(Co-Co) hexafluorophosphate
  参考文献：
  名称：

  亚胺取代的炔烃中的电荷分散：Co2（CO）6-络合的亚丙基亚胺盐的合成，光谱表征和晶体结构测定及其与不复杂配合物的结构比较

  摘要：

  In order to elucidate the charge dispersal from an iminium group onto an attached C=C bond, the crystal structures of a propyne iminium salt and its Co-2(CO)(6)-complexed analogue have been determined. For 1-(1-methyl-2-butyn-1-ylidene)pyrrolidinium triflate (3), the bond lengths of the C=C-C=N+ unit agree well with those obtained earlier by ab initio calculations; they confirm the nature of these cations as alkynyl-substituted iminium salts, with no significant resonance contribution from a beta-aminoallenyl structure. The triflate counterion is closely associated with the iminium function, and a C+-O contact smaller than the sum of the van der Waals radii is found. The first Co-2(CO)(6) complex with a propyne iminium ligand has been prepared from 3 and Co-2(CO)(8), and after anion exchange, the crystal structure of hexacarbonyl[mu-eta(4)-(1-methyl-1-(1-pyrrolidiniumylidene)-2-butyne)]dicobalt(Co-Co) hexafluorophosphate (4b) has been determined. The iminium character is preserved in this complex (C=N+ bond length 1.302(8) Angstrom), and dispersal of the positive charge onto one of the cobalt atoms is obviously not important. IR and NMR data confirm this conclusion. Salt 3, C10H14NF3O3S, crystallizes in the monoclinic space group P2(1)/c with a = 9022(3) Angstrom, b = 12.183(2) Angstrom, c = 12.013(2) Angstrom, beta = 97.73(3)degrees, and Z = 4. Cobalt complex 4b, C15H14-NCo2F6O6P, crystallizes in the orthorhombic space group Pca2(1) with a = 14.170(3) Angstrom b = 10.780(2) Angstrom, c = 13.718(3) Angstrom, and Z = 4.

  DOI：

  10.1021/om00002a062