(1,4-dithiabutanediyl-2,2'-bis(4-methylphenoxy))titanium dichloride | 856014-32-9

• 英文名称: (1,4-dithiabutanediyl-2,2'-bis(4-methylphenoxy))titanium dichloride
• CAS: 856014-32-9
• 化学式: C₁₆H₁₆Cl₂O₂S₂Ti
• 分子量: 423.22
• InChiKey: RKPOILUVZQHNTM-UHFFFAOYSA-J

反应信息

• 作为反应物：
  描述：

  (1,4-dithiabutanediyl-2,2'-bis(4-methylphenoxy))titanium dichloride 、 苄基氯化镁 以 乙醚 为溶剂， 以45%的产率得到dibenzyl(1,4-dithiabutanediyl-2,2'-bis(4-methylphenoxy))titanium
  参考文献：
  名称：

  通过包含四齿[OSSO]型双（酚基）配体的手性苄基钛配合物进行活的异特异性苯乙烯聚合

  摘要：

  二苄基配合物[Ti（OC 6 H 2 -R 1 -6-R 2 -4）2 {S（CH 2）2 S}（CH 2 Ph）2 ]（2a - c ; R 1 = t Bu，R 2 = Me中的一个; R 1，R 2 =吨卜，b ; R 1 = H，R 2 = Me中，ç）与四齿双阴离子[OSSO]型配体从相应的钛二氯络合物钛[Ti（OC合成6H 2 -R 1 -6-R 2 -4）2 {S（CH 2）2 S} Cl 2 ]和苄基氯化镁在甲苯中。NMR光谱监测所述二苄基络合物的反应的2B与B（C 6 ˚F 5）3在溴苯表示热敏苄基阳离子的形成钛[Ti（OC 6 H ^ 2 -吨卜2 -4,6-）2 {S （CH 2）2 S}（CH 2 Ph）] +。1个-30°C下的1 H NMR谱图显示55:45比率的两个C 1对称非对映异构体，表明在该温度下NMR时间尺度上的慢差向异构化。发现不带有大体积邻位取代基

  DOI：

  10.1021/om060047e
• 作为产物：
  描述：

  四氯化钛 、 1,4-dithiabutanediyl-2,2'-bis(4-methylphenol) 以 二氯甲烷 为溶剂， 以82%的产率得到(1,4-dithiabutanediyl-2,2'-bis(4-methylphenoxy))titanium dichloride
  参考文献：
  名称：

  Isospecific Styrene Polymerization by Chiral Titanium Complexes That Contain a Tetradentate [OSSO]-Type Bis(phenolato) Ligand

  摘要：

  A series of titanium dichloro and di(isopropoxy) complexes with a 1,4-dithiabutanediyl-linked bis(4,6-disubstituted phenolato) ligand [Ti(OC6H2-6-R-1-4-R-2)(2){S(CH2)(2)S}X-2] (X = Cl, 2a-i, (OPr)-Pr-i, 3a-i; R-1 = H, Me, Pr-i, Bu-t, 2-phenyl-2-propyl; R-2 = H, Me, Bu-t, OMe, 2-phenyl-2-propyl) were synthesized by reacting the corresponding linked bis(phenol) (HOC6H2-6-R-1-4-R-2)(2){S(CH2)(2)S} (1a-i) with the titanium precursor TiX4. The NMR spectra of the dichloro complexes Ti(OC6H2-6-R-1-4-R-2)(2){S(CH2)(2)S}Cl-2] (2a-d) with small ortho substituents R-1 = H, Me, Pr-i are in agreement with a C-2-symmetrical helical structure, but the complexes become fluxional at higher temperatures. The corresponding di(isopropoxy) complexes [Ti(OC6H2-6-R-1-4-R-2)(2){S(CH2)(2)S}((OPr)-Pr-i)(2)] (3a-d) are fluxional in solution at room temperature due to rapid interconversion between the Delta and Delta isomers. In contrast, both dichloro and di(isopropoxy) complexes 2e-i and 3e-i with bulky ortho substituents R-1 = Bu-t and 2-phenyl-2-propyl exhibit a rigid C2-symmetrical helical structure in solution up to 100 C. The helical structure with trans-O,O, cis-S,S, cis-Cl,Cl ("alpha-cis") is confirmed by the single-crystal structure analysis of two dichloro complexes [Ti(OC6H2-6-R-1-4-R-2)(2){S(CH2)(2)S}Cl-2] (2e, R-1 = Bu-t, R-2 = Me; 2i, R-1, R-2 = 2-phenyl-2-propyl). Related dichloro and di(isopropoxy) complexes that contain a 1,5-dithiapentanediyl-linked bis(4,6-disubstituted phenolato) ligand [Ti(OC6H2-6R(1)-4-R-2)(2){S(CH2)(3)S}X-2] (R-1 = Bu-t; R-2 = Me, Bu-t, OMe; X = Cl, 5a-c; (OPr)-Pr-i, 6a-c) were synthesized in an analogous fashion and shown by NMR spectroscopy to be conformationally flexible at room temperature. This fluxionality can be explained by a twisting of one five-membered chelate ring, converting the trans-O,O ("alpha-cis") to the cis-O,O ("beta-cis") isomer. A crystal structure determination of ligand [Ti((OC6H2Bu2)-Bu-t-4,6)(2){S(CH2)(3)S}((OPr)-Pr-i)(2)] (6b) revealed the trans-O,O, cis-S,S, cis-Cl,Cl ("alpha-cis") isomer. Upon activation with methylaluminoxane, the stereorigid derivatives 2e-i efficiently polymerize styrene to give isotactic polystyrene, whereas the conformationally flexible complexes 2a-d produce atactic polystyrene with negligible activity. Under the same conditions, complexes with the 1,5-dithiapentanediyl-linked ligand 5a,b and 6b,c polymerized styrene syndiospecifically with low activity.

  DOI：

  10.1021/om050120l