tricarbonyl(7-exo-phenylcycloheptatriene)chromium(0) | 12147-95-4

• 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: tricarbonyl(7-exo-phenylcycloheptatriene)chromium(0)
• 英文别名: Carbon monoxide;chromium;7-phenylcyclohepta-1,3,5-triene
• CAS: 12147-95-4；12147-94-3
• 化学式: C₁₆H₁₂CrO₃
• 分子量: 304.265
• InChiKey: HDTRITQUXUMRDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.34
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tricarbonyl(7-exo-phenylcycloheptatriene)chromium(0) 以 not given 为溶剂， 生成 3-C6H5C7H7Cr(CO)3
  参考文献：
  名称：

  金属辅助的1,5-西格玛移位

  摘要：

  已显示三羰基甲基环庚三烯铬的热重排遵循金属辅助的立体有规性途径，该途径涉及7-内氢原子在邻近金属原子的环表面上连续的1,5-移位。

  DOI：

  10.1039/c29700000843
• 作为产物：
  描述：

  exo-CH3OC7H7Cr(CO)3 在 苯基溴化镁 作用下， 以 乙醚 为溶剂， 生成 tricarbonyl(7-exo-phenylcycloheptatriene)chromium(0)
  参考文献：
  名称：

  环庚三烯和对硝基金属配合物。第四部分 7-外取代三羰基环庚三烯铬的制备

  摘要：

  7-外-构型分配给先前通过三羰基tropylium铬盐与阴离子的“正常”反应制备的所有取代的三羰基环庚三烯铬。描述了几个新的实例，并且表明从三羰基-7-外-甲氧基环庚三烯铬置换甲醇盐是这些产物的有利替代途径。

  DOI：

  10.1039/j39670001057

文献信息

• Cycloheptatriene and tropylium metal complexes. Part V. 7-endo-Substituted tricarbonylcycloheptatrienechromiums
  作者：P. L. Pauson、G. H. Smith、J. H. Valentine

  DOI：10.1039/j39670001061

  日期：——

  Reaction of 7-substituted cycloheptatrienes with either hexacarbonylchromium or with tricarbonyltripyridine-chromium leads to the corresponding 7-endo-substituted tricarbonylcycloheptatrienechromiums, either exclusively or, in only two of the cases studied, mixed with the exo-isomer. Some new observations on the ring-contraction of such complexes are reported.

  7-取代的环庚烯与六羰基铬或与三羰基三吡啶-铬的反应导致相应的7-内取代的三羰基环庚三烯铬单独地或仅在所研究的两种情况下与外消旋异构体混合。据报道有关这种配合物的环收缩的一些新观察。
• The stereochemistry of tricarbonylcycloheptatrienechromium derivatives
  作者：P. E. Baikie、O. S. Mills、P. L. Pauson、G. H. Smith、J. Valentine

  DOI：10.1039/c19650000425

  日期：——
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Cr: Org.Verb., 1.6.1.3.1.1, page 290 - 297
  作者：

  DOI：——

  日期：——
• Metal-Mediated [6 + 2] Cycloadditions of Alkynes to Cycloheptatriene and N-Carbethoxyazepine
  作者：Karen Chaffee、Pei Huo、John B. Sheridan、Anthony Barbieri、Arnis Aistars、Roger A. Lalancette、Robert L. Ostrander、Arnold L. Rheingold

  DOI：10.1021/ja00112a005

  日期：1995.2

  UV photolysis of [(eta(6)-C(7)H(7)R)Cr(Co)(3)] (1, R = H, Ph, CH(CO(2)Me)(2)) and R'C = CR' (R' = Ph, Tol, SiMe(3), Et) in toluene or n-hexane gives the [6 + 2] cycloadducts [(eta(2:4)-C9H7(R)R'(2))Cr(CO)(3)] (2). Heating 2 in toluene releases the 7,8-disubstituted bicyclo[4.2.1]nona-2,4,7-trienes 3 and [(eta(6)-C(6)H(5)Me)Cr(CO)(3)]. Irradiation of solutions of 1 and dimethyl acetylenedicarboxylate at 0 degrees C yields the bicyclotriene as the major product but no organometallic complex. The diphenyl derivative 2a undergoes a reversible intramolecular metal migration to the eta(6)-aryl species 4. Irradiation of the azepine complex [(eta(6)-C6H6N(CO(2)Et))Cr(CO)(3)] (5) and R'C = CR' (R' = Ph, SiMe(3)) in toluene also forms [6 + 2] cycloadducts [(eta(2:4)-C8H6N(CO2Er)R'(2))Cr(CO)(3)] (6). The heterobicyclotrienes 7 are isolated from 6 by treatment with iodine (R' = SiMe(3)) or by hearing in toluene (R' = Ph). X-ray crystal structures are reported for 6b (R' = SiMe(3)) [orthorhombic, P2(1)2(1)2(1), a = 8.871(1), b = 10.148(1), and c = 26.017(4) Angstrom, R = 0.041 for 2500 independent reflections] and a byproduct (8) that results from the endo [6 + 4] cycloaddition of N-carbethoxyazepine to 5; monoclinic, P2(1)/c, a = 10.665(9), b = 14.976(7), and c = 13.004(7) Angstrom, beta = 100.05(7)degrees, R = 0.047 for 1044 independent reflections. Heating cycloheptatriene and alkynes R'C = CR' (R' = SiMe(3), Me, Et) in dibutyl ether with a catalytic amount of Cr(CO)(6) or Fe-2(CO)(9) also gives good yields of the [6 + 2] cycloadducts 3, whereas the thermal reaction with dimethyl acetylenedicarboxylate in the presence of Cr(CO)(6) gives the known norcaradiene [4 + 2] adduct 9.
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Cr: Org.Verb., 1.6.1.8, page 305 - 307
  作者：

  DOI：——

  日期：——