(η4-cyclooctatetraene)(η8-cycloctatetraene)titanium | 12112-27-5

• 英文名称: (η4-cyclooctatetraene)(η8-cycloctatetraene)titanium
• 英文别名: bis(cyclooctatetraene)titanium；[Ti(η8-1,3,5,7-cyclooctatetraene)(η4-1,3,5,7-cyclooctatetraene)]；[Ti(COT)(η4-C8H8)]
• CAS: 12112-27-5；646059-44-1；1252659-06-5
• 化学式: C₁₆H₁₆Ti
• 分子量: 256.183
• InChiKey: VHOUAJIBVFBZLU-OGVMWVNQSA-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：

  (η4-cyclooctatetraene)(η8-cycloctatetraene)titanium 、 2-phosphaacetylene 以 甲苯 为溶剂， 以64%的产率得到(η(8)-cyclooctatetraene)((η(4)-2,4-diisopropyl(trimethylsilyl)amino)-1,3-diphosphete)titanium
  参考文献：
  名称：

  Binger, Paul; Glaser, Gerald; Albus, Stefan, Chemische Berichte, 1995, vol. 128, # 12, p. 1261 - 1266

  摘要：

  DOI：
• 作为产物：
  描述：

  1,3,5,7-cycloocatetraene 、 [Ti(N(t)Bu)(η8-1,3,5,7-cyclooctatetraene)] 在 (t)BuNC 作用下， 以 苯 为溶剂， 以70%的产率得到(η4-cyclooctatetraene)(η8-cycloctatetraene)titanium
  参考文献：
  名称：

  Synthesis and Reactions of Group 4 Imido Complexes Supported by Cyclooctatetraene Ligands

  摘要：

  The reactions of the pseudo-two-coordinate titanium imido complexes [Ti((NBu)-Bu-t)(COT)] (1) (COT = eta(8)-C8H8), [Ti((NBu)-Bu-t)(COT")] (2) (COT" = eta(8)-1,4-C8H6(SiMe3)(2)), and [Ti(NAr)(COT)] (3) (Ar = 2,6-(Pr2C6H3)-Pr-i) with a variety of organic substrates are reported. Reaction of 1 with CO2, (BuNCO)-Bu-t, or ArNCO and reaction of 3 with CO2 or (BuNCO)-Bu-t afforded the organic products (BuNCO)-Bu-t, (BuNCNBu)-Bu-t-Bu-t, (BuNCNAr)-Bu-t, ArNCO, and (ArNCNBu)-Bu-t, respectively, and a titanium oxo species. These reactions proceeded via an initial [2 + 2] cycloaddition to form an N,O-bound intermediate of the type [Ti{N(R)C(O)R'}(COT)], which subsequently underwent a retrocycloaddition to give an organic product and the titanium oxo species. In contrast, reaction of 3 with ArNCO led to the formation of the N,N-bound [2 + 2] cycloaddition product [Ti{N(Ar)C(O)N(Ar)}(COT)] (7), In general, the reactions of 1 and 3 with CS2 and isothiocyanates also resulted in an initial [2 + 2] cycloaddition to form an N,S-bound intermediate of the type [Ti{N(R)C(S)R'}(COT)], which also subsequently underwent a retrocycloaddition to give an organic product and a metal sulfide species. However, the N,S-bound compound [Ti{N(Ar)C(S)S}(COT)] (10) was stable to retrocycloaddition and was isolated. Proton transfer reactions occurred between pinacol and compounds 1-3 to form the bis(alkoxide) species [Ti{OC(Me)(2)C(Me)(2)O}(COT)] (11) (from 1 or 3) or [Ti{OC(Me)(2)C(Me)(2)O} (COT")] (12) (from 2) and the corresponding free amine. The reactions between 1-3 and 2 equiv of the thiols (BuSH)-Bu-t and HS-2,4,6-(Pr3C6H2)-Pr-i all resulted in the oxidation of the thiol to the disulfides (BuS)-Bu-t-(SBu)-Bu-t and (2,4,6-(Pr3C6H2)-Pr-i)S-S(2,4,6-(Pr3C6H2)-Pr-i). Treatment of 1 with (BuNC)-Bu-t in the presence of 1,3,5,7-cyclooctatetraene led to formal nitrene group transfer and the formation of the Ti(II) species [Ti(COT)(eta(4)-C8H8)] (13) and (BuNCNBu)-Bu-t-Bu-t. The analogous reactions between 2 and 3 and (BuNC)-Bu-t resulted in the formation of the adducts [Ti((NBu)-Bu-t)(COT")((CNBu)-Bu-t)] (15) and [Ti(NAr)(COT)((CNBu)-Bu-t)] (17), and similarly the reaction between 1 and pyridine led to the isolation of the adduct [Ti((NBu)-Bu-t)-(COT)(py)] (19) (py = pyridine). Complex 19 was crystallographically characterized. DFT studies indicated that the interaction between pyridine and the Ti center in 19 and (BuNC)-Bu-t and the Ti center in 17 was electrostatic in nature. Complexes of the type [Ti(NR)(COT)(AlMe3-xClx)] (R = Bu-t, x = 0 (20); R = Ar, x = 0 (21); R = Bu-t, x = 1 (22); R = Ar, x = 1 (23)) were formed through the reactions of 1 and 3 with AlMe3 and AlMe2Cl, and DFT studies indicated that they contained four-membered metallacyclic rings, Attempts to prepare monomeric zirconium imido cyclooctatetraene complexes through the reactions of [Zr-2(mu-NR)(2)Cl-4(THF)(x)] (R = Bu-t, x = 3; R = 2,6-Me2C6H3(Ar'), x = 4) with K2COT, Li2COT"center dot 1.8-(THF), or L-2[COT*] (COT* = 1,4-C8H6((SiMe2Bu)-Bu-t)(2)) were unsuccessful. Only the crystallographically characterized dimeric species [Zr-2(mu-NAr')(2)(COT")(2)] (24) was isolated.

  DOI：

  10.1021/om0510526