4,5-Diethylocta-3,5-diene;2,6-diphenylphenolate;titanium(2+) | 127998-83-8

• 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: 4,5-Diethylocta-3,5-diene;2,6-diphenylphenolate;titanium(2+)
• CAS: 127998-83-8
• 化学式: C₄₈H₄₆O₂Ti
• 分子量: 702.772
• InChiKey: VMABIOBGECLKBF-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  12.27
• 重原子数：
  51
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  46.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4,5-Diethylocta-3,5-diene;2,6-diphenylphenolate;titanium(2+) 以 not given 为溶剂， 生成
  参考文献：
  名称：

  一系列新的含辅助芳基氧化物配体的钛环戊烷化合物的合成，结构和动力学行为

  摘要：

  A new series of titanacyclopentane compounds have been isolated by reaction of the titanacyclopentadiene complex [Ti(OAr")2(C4Et4)] (OAr" = 2,6-diphenylphenoxide) with ethylene, propene, and 1-butene.

  DOI：

  10.1021/om00047a009
• 作为产物：
  描述：

  、 3-己炔 以 氘代苯 为溶剂， 生成 4,5-Diethylocta-3,5-diene;2,6-diphenylphenolate;titanium(2+)
  参考文献：
  名称：

  芳氧基钛化合物催化的 [2 + 2 + 2] 环加成反应区域选择性和立体选择性合成 1,3-环己二烯核

  摘要：

  各种钛芳基氧化物试剂催化两个炔烃单元与 1 当量烯烃的交叉偶联以产生 1,3-环己二烯核。催化剂包括分离的钛环戊二烯或钛环戊烷配合物。该反应通过烯烃攻击最初通过两个炔烃单元的偶联形成的钛环戊二烯化合物而进行。该反应仅限于庞大的炔烃底物，这些炔烃底物通过第三炔烃对环戊二烯钛环的竞争性攻击而进行缓慢的催化环三聚反应。分离出的有机产物通常是最初产生的 1,3-环己二烯核内异构化的结果。机理研究表明，这些异构化过程是通过在六元环的单个面上连续的、金属介导的 1,5-氢位移发生的，完全导致最终产品中的顺式立体化学。在二炔 RC⋮C(CH2)4C⋮CR (R = Et, SiMe3) 的反应中，与乙烯和 α-烯烃偶联生成...

  DOI：

  10.1021/ja970516r

文献信息

• Synthesis and Chemistry of Titanacyclopentane and Titanacyclopropane Rings Supported by Aryloxide Ligation
  作者：Matthew G. Thorn、John E. Hill、Steven A. Waratuke、Eric S. Johnson、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1021/ja970515z

  日期：1997.9.1

  = 2,6-diphenylphenoxide) with olefins leads to the formation of a variety of stable titanacyclopentane derivatives along with one equivalent of substituted 1,3-cyclohexadiene. The structural and spectroscopic properties of the ethylene product [Ti(OC6H3Ph2-2,6)2(CH2)4] (4) show a ground state titanacyclopentane structure, but facile fragmentation on the NMR time scale to form a bis(ethylene) complex

  用烯烃处理钛环戊二烯化合物 [Ti(OC6H3Ph2-2,6)2(C4Et4)] (3) (OC6H3Ph2-2,6 = 2,6-diphenylphenoxide) 导致形成各种稳定的钛环戊烷衍生物以及一当量取代的 1,3-环己二烯。乙烯产物 [Ti(OC6H3Ph2-2,6)2(CH2)4] (4) 的结构和光谱性质显示基态钛环戊烷结构，但在 NMR 时间尺度上容易碎裂形成双（乙烯）配合物已被检测到。由 α-烯烃 RCH 形成的取代产物 [Ti(OC6H3Ph2-2,6)2(C4H6R2)] (R = Me, 5; Et, 6; Ph, 7) 在烃溶液中以区域异构体和立体异构体的混合物形式存在. 对从 7 溶液获得的晶体的分析表明，反式-2,5-二苯基-钛环戊烷环以固态存在。
• The chemistry of titanacyclopentadiene rings supported by 2,6-diphenylphenoxide ligation: stoichiometric and catalytic reactivity
  作者：John E. Hill、Gary Balaich、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1021/om00032a012

  日期：1993.8

  The sodium amalgam (two Na per Ti) reduction of hydrocarbon solutions of [Ti(OAr'')2Cl2] (OAr'' = 2,6-diphenylphenoxide) in the presence of EtC=CEt, Bu(t)C=CH, and MeC=CPh (greater-than-or-equal-to2 equiv) produces the corresponding titanacyclopentadiene complexes [Ar''O)2Ti(C4Et4)] (1), [(Ar''O)2(C4H2Bu2t)] (2), and [(Ar''O)2Ti(C4Me2Ph2)] (3). The uses of less bulky substituents on the alkyne substrate in such reactions leads to mixtures of aromatic compounds due to cyclotrimerization reactions. The solid state structure of 1 shows a pseudotetrahedral environment about the titanium metal center with a planar titanacyclopentadiene ring. The H-1 and C-13 NMR spectra of solutions of 1-3 show no exchange of alpha- and beta-positions of the metallacycle rings. Only the 2,4-regioisomer and 2 and 3 was detected in solution. Reaction of 1 with PhC=CPh produced [(Ar''O)2Ti(c4Ph4)](4). reaction of 1-4 with protic reagents yielded the corresponding diene derivatives while iodination of 1 and 2 yielded 1,4-diiodo-1,3-butadienes. Compounds 1-4 will catalyze the cyclotrimerization of a range of alkynes. Terminal alkynes with small substituents produce the 1,2,4-trisubstituted benzene preferentially in an exothermic reaction. The more bulky substrates ButC=CH and Me3SiC=CH react more slowly and only the symmetrical 1,3,5-isomer is produced. The reaction of the titanacyclopentadiene rings in 1 and 2 with a ariety of unsaturated organic molecules has been investigated. Reaction of 1 with ButNC leads to a new organometallic compound 5 containing an eta2-C,N-bound cyclopentadiene-imine which was structurally characterized as a pyridine adduct (7). The solid state structure of 7 showed a structure related to other titanium eta2-C,N-bound imine complexes, but with a long Ti-C distance of 2.262(3) angstrom. Reaction of 1 or 2 with benzonitrile leads to the elimination of 1 equiv of the corresponding pyridine. The organometallic product of these reactions was identified as a dimeric material [(Ar''O)2Ti(mu-PhCN)2Ti(OAr'')2] (8) containing two bridging benzonitrile ligands. The solid state structure of 8 showed the bridging PhCN unit to be highly reduced and strongly bound to the titanium metal centers. The lack of reactivity of 8 precluded the catalytic formation of pyridines. Both compounds 1 and 2 undergo ring expansion with Ph2CO at 20-degrees-C to form the corresponding 2-oxatitanacyclohepta-4-6-diene derivatives 9 and 10. In 10 the ketone was found to insert into the side of the titanacyclopentadiene ring containing the less bulky substituent, leading to a single regioisomer. Reaction of 1 with Ph2CO at 100-degrees-C led to the 2-oxatitanacyclopent-4-ene complex [(Ar''O)2Ti(OCPh2CEtCEt)] (11) along with 1 equiv of 3-hexyne. Attempts to interconvert 9 and 11 failed. Further elaboration of the seven membered ring in 9 by reaction with ButNC yielded the eta2-iminoacyl derivative 12. The conformation of the large metallacycle rings in 9 and 12 was analyzed by carrying out single crystal X-ray diffraction analyses. Crystal data: at 20-degrees-C for TiO2C48H46 (1) a = 12.627(3) angstrom, b = 17.378(4) angstrom, C = 17.739(3) angstrom, alpha = 90.41(2)-degrees, gamma = 92.89(2)-degrees, Z = 4, d(calcd) = 1.205 g cm-3 in space group P1BAR; for TiO2N2C58H60 (7) at -105-degrees-c a = 12.554(4) angstrom, b = 17.934(5) angstrom, c = 21.567(6) angstrom, beta = 102.38(2)-degrees, Z = 4, d(calcd) = 1211 g cm-3 in space group P2(1)/n; for Ti2O4N2C98H74 (8) at -50-degrees-c a = 23.100(4) angstrom, b = 12.656(3) angstrom, c= 27.486(7) angstrom, beta = 109.09(2)-degrees, Z = 4, d(calcd) = 1.259 g cm-3 in space group C2/c; for TiO3C68H64 (9) at -50-degrees-C a = 12.147(3) angstrom, b = 12.527(3) angstrom, c = 20.363(3) angstrom, alpha = 80.92(2)-degrees, beta = 80.94(2)-degrees, gamma = 61.78(2)-degrees, Z = 2,d(calcd) = 1.204 g cm-3 in space group P1BAR for TiO3NC66H65 (12) at -20-degrees-C a = 11.774(1) angstrom, b = 22.775(3) angstrom, c = 20.137(4) angstrom, beta = 98.320(9)-degrees, Z = 4, d(calcd) = 1.203 cm-3 in space group P2(1)/NBAR.
• Hill, John E.; Fanwick, Phillip E.; Rothwell, Ian P., Inorganic Chemistry, 1991, vol. 30, # 5, p. 1143 - 1144
  作者：Hill, John E.、Fanwick, Phillip E.、Rothwell, Ian P.

  DOI：——

  日期：——
• Formation, fragmentation, and isomerization of titanacycle rings supported by aryloxide ligation
  作者：John E. Hill、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1021/om00158a017

  日期：1990.8