[Ti(N(t)Bu)(η8-1,3,5,7-cyclooctatetraene)] | 209168-02-5

• 英文名称: [Ti(N(t)Bu)(η8-1,3,5,7-cyclooctatetraene)]
• 英文别名: [Ti(N(t)Bu)(η8-C8H8)]；[Ti(N(t)Bu)(COT)]
• CAS: 209168-02-5
• 化学式: C₁₂H₁₇NTi
• 分子量: 223.154
• InChiKey: OTYIMDPSYGMFRX-AJGJWCHWSA-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：

  trimethylaluminium dimer 、 [Ti(N(t)Bu)(η8-1,3,5,7-cyclooctatetraene)] 以 苯 为溶剂， 以82%的产率得到[Ti(N(t)Bu)(η8-1,3,5,7-cyclooctatetraene)(AlMe3)]
  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
• 作为产物：
  描述：

  [Ti(N(t)Bu)(η8-1,3,5,7-cyclooctatetraene)(AlMe3)] 以 neat (no solvent, solid phase) 为溶剂， 生成 [Ti(N(t)Bu)(η8-1,3,5,7-cyclooctatetraene)]
  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

文献信息

• One- and two-step [2 + 2] cycloaddition reactions of group 4 imides with the phosphaalkyne ButCP. Crystal and molecular structures of [Zr(η5-C5H5)2(PCButNC6H3Me2-2,6)] and [TiCl2(P2C2But2NBut)(py)] (py) = pyridine)
  作者：F. Geoffrey N. Cloke、Peter B. Hitchcock、John F. Nixon、D. James Wilson、Philip Mountford

  DOI：10.1039/a900648f

  日期：——

  The structures of novel complexes resulting from one- and two-step [2 + 2] cycloaddition reactions of four group 4 imides with the phosphaalkyne ButCP are described.

  本文描述了四种第 4 组酰亚胺与膦炔丁炔发生一步式和两步式 [2 + 2] 环加成反应后产生的新型复合物的结构。
• Synthesis and molecular and electronic structure of monomeric [Ti(η8-C8H8)(NBut)]
  作者：Alexander J. Blake、Simon C. Dunn、Aidan G. Moody、Philip Mountford、Simon C. Dunn、Jennifer C. Green、Nicholas M. Jones

  DOI：10.1039/a801968a

  日期：——

  Reaction of [Ti(NBut)Cl2(py)3] with K2[C8H8] gave the monomeric, pseudo-two-coordinate complex [Ti(η8-C8H8)(NBut)] 1 which has been crystallographically characterised; the electronic structure of 1 has been investigated using density functional theory calculations and gas phase photoelectron spectroscopy.

  [Ti(NBut)Cl2(py)3]与 K2[ ] 反应生成了单质假双配位复合物[Ti(δ-8-C8H8)(NBut)] 1，并对其进行了晶体学表征；利用密度泛函理论计算和气相光电子能谱对 1 的电子结构进行了研究。
• Reactions of ^tBuC⋮P with Cyclooctatetraene-Supported Titanium Imido Complexes
  作者：F. Geoffrey N. Cloke、Jennifer C. Green、Nilay Hazari、Peter B. Hitchcock、Philip Mountford、John F. Nixon、D. James Wilson

  DOI：10.1021/om060273o

  日期：2006.7.1

  Reaction of the pseudo two-coordinate titanium imido complexes [Ti((NBu)-Bu-t)(COT)] (1; COT) eta(8)-C8H8) and [Ti((NBu)-Bu-t)(COT")] (2; COT") eta(8)-1,4-C8H6(SiMe3)(2)) with 2 equiv of (t)BuCt P generated the new complexes [Ti N(Bu-t) PC(Bu-t) PC(Bu-t)}(COT)] (4) and [Ti N(Bu-t) PC(Bu-t) PC(Bu-t)}(COT")] (5), respectively. Complex 4 was crystallographically characterized, and a density functional theory (DFT) study combined with photoelectron (PE) spectroscopy revealed this apparently 20-valence-electron species to contain a HOMO which is almost entirely ligand-based. In contrast, the organic compound N(Ar)(P2C2Bu2)-Bu-t (6), which incorporates a 1,2,4-azadiphosphole ring, was the only isolated product from the reaction of the arylimido species [Ti(NAr)(COT)] (3; Ar) 2,6-(Pr2C6H3)-Pr-i) with an excess of (BuC)-Bu-t P. DFT studies indicated that the mechanisms for the formation of compounds 4 - 6 are similar. Initially, one molecule of (BuC)-Bu-t P undergoes a [2 + 2] cycloaddition with [Ti(NR)(COT)] to form [TiN(R)PC(Bu-t)}(COT)], which contains a Ti-C bond. Subsequently, a second molecule of (BuC)-Bu-t P reacts with [TiN(R)PC(Bu-t)}(COT)] to form [TiN(R)PC(Bu-t)PC(Bu-t)}(COT)]. When R = 2,6-(Pr2C6H3)-Pr-i or a substituent which is less sterically bulky, the formation of a heterocyclic ring such as N(Ar)(P2C2Bu2)-Bu-t (6) is favored. However, when R = Bu-t, it is sterically unfavorable to form such a ring and thus compound 4 is stable.