((1,2,11,12-η)-tricyclo[10.8.0.0(2,11)]eicosa-1,11-diene-6,17-diyne)(η(5)-cyclopentadienyl)cobalt

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: ((1,2,11,12-η)-tricyclo[10.8.0.0(2,11)]eicosa-1,11-diene-6,17-diyne)(η(5)-cyclopentadienyl)cobalt
• 化学式: C₂₅H₂₉Co
• 分子量: 388.498
• InChiKey: LRAMLYPSVVGZPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.33
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  carbon monoxide,cobalt,cyclopenta-1,3-diene 、 ((1,2,11,12-η)-tricyclo[10.8.0.0(2,11)]eicosa-1,11-diene-6,17-diyne)(η(5)-cyclopentadienyl)cobalt 以 萘烷 为溶剂， 以80%的产率得到(η(4):η(4)-[3(4)]cyclobutadienophane)bis(η(5)-cyclopentadienyl)cobalt
  参考文献：
  名称：

  Synthesis and Properties of Donor-Acceptor-Substituted Metal-Capped Fourfold-Bridged Cyclobutadienophanes

  摘要：

  The synthesis of the superphanes 4-8 could be achieved from {(1,2,11,12-eta(4))-tricyclo[10.8.0.0(2,11)]eicosa-1, 11-diene-6,17-diyne}(eta(5)-cyclopentadienyl (15) and its methoxycarbonyl congener 14 by heating with R-CpCo(CO)(2) (R = H, CH3, (CH3)(5)). X-ray investigations on the superphanes 3, 6, and 8 reveal distances between the two cyclobutadiene units between 2.922 Angstrom (3) and 2.941 Angstrom (6). Investigations by means of cyclic voltammetry show a decrease of the first oxidation potentials with increasing number of CH3 substituents at the cyclopentadienyl ligands. The comparison between the first oxidation potentials of 2-6, 4-7, and 5-8 gives evidence for a partial charge delocalization over both CpCoCb fragments of the superphanes.

  DOI：

  10.1021/om9907270
• 作为产物：
  描述：

  在 BuLi 、 MeOH 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以71%的产率得到((1,2,11,12-η)-tricyclo[10.8.0.0(2,11)]eicosa-1,11-diene-6,17-diyne)(η(5)-cyclopentadienyl)cobalt
  参考文献：
  名称：

  Stepwise Approach to Metal-Capped 4-Fold-Bridged Cyclobutadienophanes

  摘要：

  The three cyclic alkynes 5-cyclononynol (31), 5-cyclodecynol (15), and 6-cycloundecynol (16) are dimerized with CpCo(COD) to the tricyclic dialcohols 17, 24, and 32, respectively. Oxidation of the alcohols yields the diketones 18, 19, 25, and 33 which can be transformed to the tricyclic diynes 23, 29, 30, and 36 via the bis(selenadiazole)s. Reaction of 23 with CpCo(CO)(2), Cp*Co(CO)(2), and Fe(CO)(5) yields superphanes in which both complexed cyclobutadiene (Cb) units are connected with four trimethylene chains. The reaction of 29/30 with CpCo(CO)(2) affords two isomeric CpCo-stabilized fourfold-bridged bicyclo[4.2.0]octa-2,4,7-dienes 43 and 44 besides the expected superphane 42 in which the CpCo-capped Cb units are connected by two trimethylene and two tetramethylene chains. The key compounds, tricyclic diynes 23 and 36, superphane 40, and bicyclooctatriene 44, have been characterized using X-ray structural analysis. Crystal data: 23, C25H29Co, triclinic, space group C-i(1), P $($) over bar$$ 1 (No. 2), a = 9.003 Angstrom, b = 10.399 Angstrom, c = 11.874 Angstrom, alpha = 93.45 degrees, beta = 101.45 degrees, gamma = 108.77 degrees, V = 1022.34 Angstrom(3), Z = 2; 36, C23H25CO, rhombic, space group D-2(4), P2(1)2(1)2(1) (NO. 19), a = 9.555(9) Angstrom, b = 12.86(1) Angstrom, c = 15.551(9) V = 1910.9 Angstrom(3), Z = 4; 40, C28H29CoFeO3, monoclinic, space group C-s(4), Cc (No. 9), a = 18.92(1) Angstrom, b = 8.499(6) Angstrom, c = 19.37(1) Angstrom, beta = 130.16 degrees, V = 2380.41 Angstrom(3), Z = 4; 44, C27H33Co, triclinic, space group C-i(1), P $($) over bar$$ 1 (No. 2), a = 8.269(3) Angstrom, b = 9.082(2) Angstrom, c = 13.72.4 Angstrom, a = 84.87(2)degrees, beta = 88.77(3)degrees, gamma = 80.62(2)degrees, V = 1012.8 Angstrom(3), Z = 2.

  DOI：

  10.1021/om00002a051

文献信息

• Superphanes with CpCo-Stabilized Cyclopentadienone Units. Synthesis and Properties
  作者：Rolf Roers、Frank Rominger、Bernhard Nuber、Rolf Gleiter

  DOI：10.1021/om991000e

  日期：2000.4.1

  The cyclic alkynes 5-cyclononynone (23) and 5-cyclodecynone (24) were dimerized by heating with CpCo(CO)2 to form the tricyclic CpCo-stabilized cyclopentadienone derivatives 25 and 26, respectively. These diketones were transformed to the tricyclic diynes 30, 31, and 33, via the corresponding bis(selenadiazoles). Whereas the diynes 30 and 31 did not yield the desired bis(cyclopentadienono)phanes, we

  通过与CpCo（CO）2加热，将环状炔烃5-环壬酮（23）和5-环癸酮（24）二聚，分别形成三环CpCo-稳定的环戊二烯酮衍生物25和26。这些二酮转化到三环二炔30，31，和33通过相应的双（selenadiazoles）。尽管二炔30和31无法产生所需的双（环戊二烯基）phanes，但我们成功地获得了33。在CpCo（CO）2存在下加热33在150℃下产生分子内环加成产物34和混合的超显像35。在5°C下在CpCo（CO）2存在下辐照33产生2倍CpCo封端的双（环戊二烯）Superphane 44。该反应顺序，所述的关键化合物26A，31，33，34，和44，已通过X射线结构分析。
• Gleiter, Rolf; Schehlmann, Volker, Angewandte Chemie, 1990, vol. 102, p. 1450 - 1452
  作者：Gleiter, Rolf、Schehlmann, Volker

  DOI：——

  日期：——
• Synthesis and Properties of Donor-Acceptor-Substituted Metal-Capped Fourfold-Bridged Cyclobutadienophanes
  作者：Rolf Gleiter、Rolf Roers、Jörg Classen、Albrecht Jacobi、Gottfried Huttner、Thomas Oeser

  DOI：10.1021/om9907270

  日期：2000.1.1

  The synthesis of the superphanes 4-8 could be achieved from (1,2,11,12-eta(4))-tricyclo[10.8.0.0(2,11)]eicosa-1, 11-diene-6,17-diyne}(eta(5)-cyclopentadienyl (15) and its methoxycarbonyl congener 14 by heating with R-CpCo(CO)(2) (R = H, CH3, (CH3)(5)). X-ray investigations on the superphanes 3, 6, and 8 reveal distances between the two cyclobutadiene units between 2.922 Angstrom (3) and 2.941 Angstrom (6). Investigations by means of cyclic voltammetry show a decrease of the first oxidation potentials with increasing number of CH3 substituents at the cyclopentadienyl ligands. The comparison between the first oxidation potentials of 2-6, 4-7, and 5-8 gives evidence for a partial charge delocalization over both CpCoCb fragments of the superphanes.
• Stepwise Approach to Metal-Capped 4-Fold-Bridged Cyclobutadienophanes
  作者：Rolf Gleiter、Heinrich Langer、Volker Schehlmann、Bernhard Nuber

  DOI：10.1021/om00002a051

  日期：1995.2

  The three cyclic alkynes 5-cyclononynol (31), 5-cyclodecynol (15), and 6-cycloundecynol (16) are dimerized with CpCo(COD) to the tricyclic dialcohols 17, 24, and 32, respectively. Oxidation of the alcohols yields the diketones 18, 19, 25, and 33 which can be transformed to the tricyclic diynes 23, 29, 30, and 36 via the bis(selenadiazole)s. Reaction of 23 with CpCo(CO)(2), Cp*Co(CO)(2), and Fe(CO)(5) yields superphanes in which both complexed cyclobutadiene (Cb) units are connected with four trimethylene chains. The reaction of 29/30 with CpCo(CO)(2) affords two isomeric CpCo-stabilized fourfold-bridged bicyclo[4.2.0]octa-2,4,7-dienes 43 and 44 besides the expected superphane 42 in which the CpCo-capped Cb units are connected by two trimethylene and two tetramethylene chains. The key compounds, tricyclic diynes 23 and 36, superphane 40, and bicyclooctatriene 44, have been characterized using X-ray structural analysis. Crystal data: 23, C25H29Co, triclinic, space group C-i(1), P $($) over bar$$ 1 (No. 2), a = 9.003 Angstrom, b = 10.399 Angstrom, c = 11.874 Angstrom, alpha = 93.45 degrees, beta = 101.45 degrees, gamma = 108.77 degrees, V = 1022.34 Angstrom(3), Z = 2; 36, C23H25CO, rhombic, space group D-2(4), P2(1)2(1)2(1) (NO. 19), a = 9.555(9) Angstrom, b = 12.86(1) Angstrom, c = 15.551(9) V = 1910.9 Angstrom(3), Z = 4; 40, C28H29CoFeO3, monoclinic, space group C-s(4), Cc (No. 9), a = 18.92(1) Angstrom, b = 8.499(6) Angstrom, c = 19.37(1) Angstrom, beta = 130.16 degrees, V = 2380.41 Angstrom(3), Z = 4; 44, C27H33Co, triclinic, space group C-i(1), P $($) over bar$$ 1 (No. 2), a = 8.269(3) Angstrom, b = 9.082(2) Angstrom, c = 13.72.4 Angstrom, a = 84.87(2)degrees, beta = 88.77(3)degrees, gamma = 80.62(2)degrees, V = 1012.8 Angstrom(3), Z = 2.