[Ti(MeC(2-C5H4N)(CH2N-3,5-C6H3Me2)2)(κ2-N(tBu)CH=CTol)] | 959627-87-3

• 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(MeC(2-C5H4N)(CH2N-3,5-C6H3Me2)2)(κ2-N(tBu)CH=CTol)]
• 英文别名: [Ti(MeC(2-C5H4N)(CH2N(3,5-C6H3Me2))2)(κ2-N(t-Bu)CH=C-4-C6H4Me)]
• CAS: 959627-87-3
• 化学式: C₃₈H₄₆N₄Ti
• 分子量: 606.69
• InChiKey: SUHYVZGOMPONNB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [Ti(MeC(2-C5H4N)(CH2N-3,5-C6H3Me2)2)(κ2-N(tBu)CH=CTol)] 、 异氰酸叔丁酯 以 甲苯 为溶剂， 以99%的产率得到[Ti(MeC(2-C5H4N)(CH2N(3,5-C6H3Me2))2)(κ2-N(t-Bu)CH=C(Tol)C=N(t-Bu))]
  参考文献：
  名称：

  Insertions into Azatitanacyclobutenes: New Insights into Three-Component Coupling Reactions Involving Imidotitanium Intermediates

  摘要：

  Reaction of the titanium imido complexes [Ti(NR)((N2Npy)-N-Xyl)(L)] ((N2Npy)-N-Xyl = MeC(2-C5H4N){CH2N(3,5-C6H3Me2)}(2)) with aryl acetylenes afforded the {2+2} cycloaddition products [Ti((N2Npy)-N-Xyl) {kappa(2)-N(Bu-t)CH=CAr}] (Ar = Ph: 1a, Tol: 1b (Tol = 4-C6H4Me)). Complex la was found to insert sulfur and selenium atoms into the Ti-C bond of the strained azatitanacyclobutene unit to give the five-membered metallacyclic systems [Ti((N2Npy)-N-Xyl){kappa(2)-N(Bu-t)CH=C(Ph)E}] (E = S: 2, Se: 3). Likewise, isonitriles were found to insert into the Ti-C bonds to give [Ti((N2Npy)-N-Xyl){kappa(2)-N(Bu-t)CH=C(Ar)C=NR}] (Ar = Ph, R = xylyl: 4, Cy: 5, Bu-t: 6a; Ar = C6H5Me, R = Bu-t: 6b), one example of which (4) has been characterized by X-ray crystallography. The latter species is thought to be a key intermediate in the titanium-mediated three-component coupling of primary amines with acetylenes and isonitriles ("iminoamination"). Reaction of [Ti(N2(Xyl)N(py)){kappa(2)-N(Bu-t)CH=C(Ph)C=NR}] with (BuNH2)-Bu-t gave (BuN)-Bu-t=CHC(Ph)CHNHR, which have been previously identified as the major reaction products in the catalytic aminoamination of alkynes.

  DOI：

  10.1021/om8001203
• 作为产物：
  描述：

  [Ti(N(t)Bu)(MeC(2-C5H4N)(CH2N-3,5-C6H3Me2)2)(pyridine)] 、 乙烷,三氯氟- 以 甲苯 为溶剂， 以52%的产率得到[Ti(MeC(2-C5H4N)(CH2N-3,5-C6H3Me2)2)(κ2-N(tBu)CH=CTol)]
  参考文献：
  名称：

  Imido-Alkyne Coupling in Titanium Complexes:  New Insights into the Alkyne Hydroamination Reaction

  摘要：

  Titanium imido complexes [Ti(NR)((N2Npy)-N-Ar)(L)](N(2)AN(py) = MeC(2-C5H4N)(CH2NAr)(2), Ar = 4-C6H4Me or 3,5-C6H3Me2) have been prepared from the corresponding bis(amide) complexes [Ti((N2Npy)-N-Ar) (NMe2)(2)]. The reaction chemistry of the imido ligand has been investigated with aryl acetylenes, affording the { 2 + 2} cycloaddition products [Ti((N2Npy)-N-Ar){kappa(2)-N('Bu)CH=CAr'}] (Ar'= Ph and 4-C6H4Me) which represent a catalytic intermediate in the anti-Markovnikov hydroamination of terminal alkynes. Reaction of these azatitanacyclobutene complexes with tert-butylamine completes the catalytic cycle, affording trans-cinnamyl(tert-butyl)amine; conversely, reaction with a second equivalent of alkyne afforded a second insertion product, an azatitanacyclohexadiene [Ti(N2Npy){kappa(2)-N('Bu)CH=C(Ar')C(Ar') = CH}], two examples of which have been characterized by X-ray crystallography. Studies into the catalytic hydroamination of phenyl acetylene with tert-butylamine have been performed and indicate that the formation of an azatitanacyclohexadiene complex represents a deactivation pathway in this catalytic reaction.

  DOI：

  10.1021/om700758v