| 1555968-24-5

• CAS: 1555968-24-5
• 化学式: C₄₂H₄₈F₈N₄O₂Ti
• 分子量: 840.736
• InChiKey: UIUMKVPUJKNSMW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  以 苯 为溶剂， 反应 18.0h， 以90%的产率得到
  参考文献：
  名称：

  Reactions of a Cyclopentadienyl–Amidinate Titanium Benzimidamido Complex

  摘要：

  We report the first reactivity study of a transition-metal benzimidamido complex, namely Cp*Ti{PhC((NPr)-Pr-i)(2)}{NC(Ar-F5)(NOBu)-Bu-t} (5, Ar-F5 = C6F5). Reaction with CO2 and (BuNCO)-Bu-t gave the cycloaddition products Cp*Ti[PhC((NPr)-Pr-i)(2)}{OC(O)N(C{(ArNOBu)-N-F5-Bu-t)} and Cp*Ti[PhC((NPr)-Pr-i)(2)}{OC((NBu)-Bu-t)N(C{Ar-F5}(NOBu)-Bu-t)} (10), respectively, whereas with CS2 slow extrusion of ArFcCN from 5 occurred to ultimately form Cp*Ti{PhC((NPr)-Pr-i)(2)}{SC(S)N((OBu)-Bu-t)}. Reaction of 5 with ArC(O)H (Ar = Ph, 4-C6H4Me, 4-(C6H4Bu)-Bu-t, 4-C6H4OMe, 4-C6H4NMe2, 4-C6H4CF3) also gave the isolable metallacyclic complexes Cp*Ti{PhC(NiPr)(2)}[N(C{Ar-F5}(NOBu)-Bu-t)C(Ar)(H)O} (13) via reversible [2 + 2] cycloaddition reactions. In contrast, reaction with HC(O)NMe2 formed Me2N{NC(Ar-F5)(NOBu)-Bu-t}H (16) within 1 h at room temperature. Upon heating, 10 and 13 also underwent retrocyclization, forming the organic products (BuNCNC)-Bu-t(Ar-F5)(NOBu)-Bu-t and ArC{NC(Ar-F5)(NOBu)-Bu-t}H (14), respectively. Selected examples of 14 and 16 were studied by DFT and UV visible spectroscopy. Addition of isonitriles (BuNC)-Bu-t and XyINC (Xyl = 2,6-C6H3Me2) to Cp*Ti{PhC(NiPr)(2)}{NC(Ar)(NOBu)-Bu-t} (Ar = Ar-F5 (5), 2,6-C6H3F2 (Ar-F2)) afforded the sigma adducts Cp*Ti{PhC((NPO2)-P-i}{NC(Ar)(NOBu)-Bu-t}(CNR) (Ar = ArF5, R = Bu-t, Xyl (19); Ar = Ar-F2, R = Xyl). Subsequently, 19 formed Cp*Ti{PhC((NPr)-Pr-i)(2)}{NC((NOBu)-Bu-t)C6F4N(Xyl)C}(F) (20) via C-F bond activation. Reaction of 5 with 2 equiv of B(Ar-F5)3 gave Cp*Ti{PhC((NPr)-Pr-i)(2)}{ON(B{Ar-F5}(3))C(Ar-F5)N(H)(B{Ar-F5}}(3))} with elimination of 2-methylpropene.

  DOI：

  10.1021/om4011752
• 作为产物：
  描述：

  对三氟甲基苯甲醛 、 以 苯 为溶剂， 反应 0.5h， 以99%的产率得到
  参考文献：
  名称：

  Reactions of a Cyclopentadienyl–Amidinate Titanium Benzimidamido Complex

  摘要：

  We report the first reactivity study of a transition-metal benzimidamido complex, namely Cp*Ti{PhC((NPr)-Pr-i)(2)}{NC(Ar-F5)(NOBu)-Bu-t} (5, Ar-F5 = C6F5). Reaction with CO2 and (BuNCO)-Bu-t gave the cycloaddition products Cp*Ti[PhC((NPr)-Pr-i)(2)}{OC(O)N(C{(ArNOBu)-N-F5-Bu-t)} and Cp*Ti[PhC((NPr)-Pr-i)(2)}{OC((NBu)-Bu-t)N(C{Ar-F5}(NOBu)-Bu-t)} (10), respectively, whereas with CS2 slow extrusion of ArFcCN from 5 occurred to ultimately form Cp*Ti{PhC((NPr)-Pr-i)(2)}{SC(S)N((OBu)-Bu-t)}. Reaction of 5 with ArC(O)H (Ar = Ph, 4-C6H4Me, 4-(C6H4Bu)-Bu-t, 4-C6H4OMe, 4-C6H4NMe2, 4-C6H4CF3) also gave the isolable metallacyclic complexes Cp*Ti{PhC(NiPr)(2)}[N(C{Ar-F5}(NOBu)-Bu-t)C(Ar)(H)O} (13) via reversible [2 + 2] cycloaddition reactions. In contrast, reaction with HC(O)NMe2 formed Me2N{NC(Ar-F5)(NOBu)-Bu-t}H (16) within 1 h at room temperature. Upon heating, 10 and 13 also underwent retrocyclization, forming the organic products (BuNCNC)-Bu-t(Ar-F5)(NOBu)-Bu-t and ArC{NC(Ar-F5)(NOBu)-Bu-t}H (14), respectively. Selected examples of 14 and 16 were studied by DFT and UV visible spectroscopy. Addition of isonitriles (BuNC)-Bu-t and XyINC (Xyl = 2,6-C6H3Me2) to Cp*Ti{PhC(NiPr)(2)}{NC(Ar)(NOBu)-Bu-t} (Ar = Ar-F5 (5), 2,6-C6H3F2 (Ar-F2)) afforded the sigma adducts Cp*Ti{PhC((NPO2)-P-i}{NC(Ar)(NOBu)-Bu-t}(CNR) (Ar = ArF5, R = Bu-t, Xyl (19); Ar = Ar-F2, R = Xyl). Subsequently, 19 formed Cp*Ti{PhC((NPr)-Pr-i)(2)}{NC((NOBu)-Bu-t)C6F4N(Xyl)C}(F) (20) via C-F bond activation. Reaction of 5 with 2 equiv of B(Ar-F5)3 gave Cp*Ti{PhC((NPr)-Pr-i)(2)}{ON(B{Ar-F5}(3))C(Ar-F5)N(H)(B{Ar-F5}}(3))} with elimination of 2-methylpropene.

  DOI：

  10.1021/om4011752