[Ti(OC6H3Ph2-2,6)2Cl2] | 110300-61-3

• 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: [Ti(OC6H3Ph2-2,6)2Cl2]
• 英文别名: 2,6-Diphenylphenolate;titanium(4+);dichloride
• CAS: 110300-61-3
• 化学式: C₃₆H₂₆Cl₂O₂Ti
• 分子量: 609.387
• InChiKey: SUMYKZPINHJJTQ-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  2.19
• 重原子数：
  41
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  46.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [Ti(OC6H3Ph2-2,6)2Cl2] 在 sodium amalgam 作用下， 以 苯 为溶剂， 生成
  参考文献：
  名称：

  The chemistry of titanacyclopentadiene rings supported by 2,6-diphenylphenoxide ligation: stoichiometric and catalytic reactivity

  摘要：

  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.

  DOI：

  10.1021/om00032a012
• 作为产物：
  描述：

  2,6-二苯基苯酚 、 四氯化钛 以 甲苯 为溶剂， 以90%的产率得到[Ti(OC6H3Ph2-2,6)2Cl2]
  参考文献：
  名称：

  A bis(trimethylstannyl)amido complex of titanium. The synthesis and structures of [TiCl2(OC6H3Ph2-2,6)2] and [TiCl{N(SnMe3)2}(OC6H3Ph2-2,6)2]

  摘要：

  DOI：

  10.1016/0022-328x(86)80421-1
• 作为试剂：
  描述：

  1-庚烯-6-炔 在 sodium amalgam 、 正丁基锂 、 [Ti(OC6H3Ph2-2,6)2Cl2] 作用下， 以 四氢呋喃 为溶剂， 反应 6.75h， 生成 (1Z)-1-(2-methylcyclopentylidene)-2-methylidenecyclopentane
  参考文献：
  名称：

  Novel, stereoselective tricyclization of a dienyne by titanium aryloxide centers

  摘要：

  通过分子内将烯烃插入钛五环-2-烯的钛-乙烯基键，由芳基氧化物连接支持的钛中心介导了二炔的三环化反应。

  DOI：

  10.1039/b209889j

文献信息

• Trichloro monophenoxide complexes of titanium(IV)
  作者：Alastair J. Nielson、Peter Schwerdtfeger、Joyce M. Waters

  DOI：10.1039/a908435e

  日期：——

  Thermalisation of TiCl4 and phenol (1∶1) in toluene gave [TiCl3(OC6H5)] 1. The more soluble complex [TiCl3(OC6H4CMe3-4)] 2 is monomeric in benzene and reacts with 4,4′-dimethyl-2,2′-bipyridyl (dmbipy) to give mer-[TiCl3(OC6H4CMe3-4)(dmbipy)] 3 and the disproportionation product [TiCl2(OC6H4CMe3-4)2(dmbipy)]. The complex [TiCl3(OC6H2Me3-2,4,6)] 4 is monomeric in benzene whereas [TiCl3(OC6H3Pri2-2,6)] 5 partially disproportionates in solution into [TiCl2(OC6H3Pri2-2,6)2] and reacts with dmbipy to give mer-[TiCl3(OC6H3Pri2-2,6)(dmbipy)] 6 and [TiCl2(OC6H3Pri2-2,6)2(dmbipy)]. Thermalisation of 2,6-di-tert-butyl-4-methylphenol and TiCl4 in toluene caused debutylation but [TiCl3OC6H2(CMe3)2-2,6-Me-4}] 7 forms in light petroleum (bp range 40–60 °C). Complex 7 is monomeric in benzene and does not form adducts with dmbipy or other sigma donors. A crystal structure determination of 7 showed a monomer with distorted tetrahedral co-ordination, a Ti–O bond length of 1.750(2) Å and Ti–Cl bonds longer than in TiCl4 but shorter than in [TiCl3(C5H5)] or [TiCl3C5H3(CMe3)2-1,3}]. 2,4,6-Tri-tert-butylphenol debutylates when thermalised with TiCl4 in toluene giving [TiCl3OC6H4(CMe3)2-2,4} ] 8. The complexes [TiCl3OC6H2(CMe3)2-2,6-OMe-4}] 9, [TiCl3(OC6H3CMe3-2-Me-4)] 10, [TiCl3(OC6H4Ph-2)] 11 and the 1-naphthoxide complex [TiCl3(OC10H7)] 12 were also prepared. Density functional calculations performed on the models 4 and [TiCl3(OMe)] showed both lone pairs on oxygen donate electron density to titanium but O(2p)-to-CC (π*) donation weakens the Ti–O interaction in the phenoxide complex; Cl(2p)-to-Ti(3d) donation is much reduced in the methoxide complex. The system [TiCl3(OC6H4CMe3-4)]/AlMe3 is 280 times more active than [TiCl3Cp] (Cp = cyclopentadienyl)/AlMe3 for low pressure (6 psi) ethylene polymerisation but  1//3 less active than TiCl4/AlMe3.

  将TiCl4和苯酚（1∶1）在甲苯中加热得到[TiCl3(OC6H5)] 1。在苯中，更易溶的复合物[TiCl3(OC6H4CMe3-4)] 2是单体的，并与4,4′-二甲基-2,2′-联吡啶（dmbipy）反应生成mer-[TiCl3(OC6H4CMe3-4)(dmbipy)] 3和歧化产物[TiCl2(OC6H4CMe3-4)2(dmbipy)]。复合物[TiCl3(OC6H2Me3-2,4,6)] 4在苯中是单体的，而[TiCl3(OC6H3Pri2-2,6)] 5在溶液中部分歧化成[TiCl2(OC6H3Pri2-2,6)2]，并与dmbipy反应生成mer-[TiCl3(OC6H3Pri2-2,6)(dmbipy)] 6和[TiCl2(OC6H3Pri2-2,6)2(dmbipy)]。将2,6-二叔丁基-4-甲基苯酚和TiCl4在甲苯中加热导致脱叔丁基反应，但在石油醚（沸点范围40–60°C）中形成[TiCl3OC6H2(CMe3)2-2,6-Me-4}] 7。复合物7在苯中是单体的，并且不与dmbipy或其他σ供体形成加合物。对7的晶体结构测定显示为扭曲的四面体配位单体，Ti–O键长为1.750(2) Å，Ti–Cl键长于TiCl4但短于[TiCl3(C5H5)]或[TiCl3C5H3(CMe3)2-1,3}]。2,4,6-三叔丁基苯酚在甲苯中与TiCl4加热时脱叔丁基生成[TiCl3OC6H4(CMe3)2-2,4}] 8。还制备了复合物[TiCl3OC6H2(CMe3)2-2,6-OMe-4}] 9、[TiCl3(OC6H3CMe3-2-Me-4)] 10、[TiCl3(OC6H4Ph-2)] 11和1-萘酚复合物[TiCl3(OC10H7)] 12。对模型4和[TiCl3(OMe)]进行的密度泛函计算表明氧上的孤对电子向钛捐赠电子密度，但O(2p)-到CC（π*）的捐赠削弱了酚酸盐复合物中的Ti–O相互作用；在甲氧基复合物中Cl(2p)-到Ti(3d)的捐赠大大减少。系统[TiCl3(OC6H4CMe3-4)]/AlMe3对于低压（6 psi）乙烯聚合的活性是[TiCl3Cp]（Cp = 环戊二烯基）/AlMe3的280倍，但活性是TiCl4/AlMe3的1/3。
• Regio- and stereo-selective coupling reactions of cyclo-1,3-dienes catalysed by titanium aryloxide compounds
  作者：Steven A. Waratuke、Eric S. Johnson、Matthew G. Thorn、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1039/cc9960002617

  日期：——

  Highly selective non-Diels–Alder dimerization of cyclohexa-1,3-diene and cross-coupling of either cyclohexa-1,3-diene or cycloocta-1,3-diene with α-alkenes is catalysed by titanium aryloxide compounds.

  钛芳氧化物化合物催化环己烯-1,3-二烯的高度选择性非Diels–Alder二聚反应，以及环己烯-1,3-二烯或环辛烯-1,3-二烯与α-烯烃的交叉偶联反应。
• Trimerization of <i>tert</i>-Butylacetylene to 1,3,6-Tri(<i>tert</i>-butyl)fulvene Catalyzed by Titanium Aryloxide Compounds
  作者：Eric S. Johnson、Gary J. Balaich、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1021/ja972306k

  日期：1997.11.1

  scattered reports of the stoichiometric conversion of three alkyne units into the fulvene nucleus via a formal [2+2+1] cycloaddition.3,4 In this paper, we report on our initial synthetic and mechanistic studies of a titanium aryloxide catalyst system which selectively converts tert-butylacetylene into the corresponding fulvene.

  炔烃链段的 [2 + 2 + 2] 环加成生成芳烃核是有机过渡金属化学中最普遍和研究最多的反应之一。 1,2 相比之下，只有零星报道三种化学计量转化炔单元通过正式的 [2+2+1] 环加成进入富烯核。 3,4 在本文中，我们报告了我们对芳氧基钛催化剂体系的初步合成和机理研究，该体系选择性地将叔丁基乙炔转化为相应的富烯.
• Cationic Group 4 metal alkyl compounds containing aryloxide ligation: synthesis, structure, reactivity and polymerization studies
  作者：Matthew G Thorn、Zac C Etheridge、Phillip E Fanwick、Ian P Rothwell

  DOI：10.1016/s0022-328x(99)00409-x

  日期：1999.12

  A series of bis(alkyl) derivatives of titanium and zirconium [(ArO)2MR2] (M=Ti, Zr; R=Me, CH2Ph; ArO=various 2,6-di-substituted phenoxides) has been synthesized and their reactivity towards the Lewis acid [B(C6F5)3] examined. The benzyl compounds generate stable zwitterionic species such as [M(OC6HPh2-2,6-R2-3,5)2(CH2Ph)][η6-C6H5CH2B(C6F5)3] (M=Ti, R=H, 12; Me, 13: M=Zr, R=Me, 15). Structural studies

  合成了一系列钛和锆的双（烷基）衍生物[（ArO）2 MR 2 ]（M = Ti，Zr; R = Me，CH 2 Ph; ArO =各种2,6-二取代的酚盐）以及它们对路易斯酸[B（C 6 F 5）3 ]的反应性。的苄基化合物产生稳定的两性离子物质如[M（OC 6 HPH 2 -2,6-R 2 -3,5-）2（CH 2 PH）] [η 6 -C 6 H ^ 5 CH 2 B（C 6 ˚F 5）3 ]（M = Ti，R = H，12; Me，13：M ＝ Zr，R ＝ Me，15）。对12和15的结构研究表明，硼阴离子通过原始的苄基苯基环与金属中心π结合。相反，用[B（C 6 F 5）3 ]处理苄基化合物[Zr（OC 6 H 3 Bu t 2 -2,6）2（CH 2 Ph）2 ]会导致环金属化的化合物[Zr（ OC 6 H 3 Bu t -CMe 2 CH 2）（OC 6 H 3 Bu吨2 -2
• 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。