Ti(S-t-Bu)4

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: Ti(S-t-Bu)4
• 英文别名: 2-Methylpropane-2-thiolate;titanium(4+)；2-methylpropane-2-thiolate;titanium(4+)
• 化学式: C₁₆H₃₆S₄Ti
• 分子量: 404.606
• InChiKey: XQNKKUHIOKMUDM-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  5.32
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Ti(S-t-Bu)4 以 neat (no solvent) 为溶剂， 生成 titanium monosulfide
  参考文献：
  名称：

  挥发性Ti（SBu t）4对TiS薄膜的热沉积

  摘要：

  TiS的非晶态膜是通过在130–200°C的条件下对Ti（SBu t）4进行低压蒸汽相热解而沉积的。

  DOI：

  10.1039/c39880000344
• 作为产物：
  描述：

  [Ti(N(t)Bu)(η8-1,3,5,7-cyclooctatetraene)] 、 叔丁基硫醇 以 氘代苯 为溶剂， 生成 Ti(S-t-Bu)4
  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

• Thiolate derivatives of titanium(iv) and tantalum(v) as precursors to metal sulfides
  作者：Claire J. Carmalt、Christopher W. Dinnage、Ivan P. Parkin、Andrew J. P. White、David J. Williams

  DOI：10.1039/b104888k

  日期：——

  Reaction of Ta(NMe2)5 with 10 equivalents of 2,6-Me2C6H3SH in toluene resulted in the formation of bright red crystals of [Ta(SC6H3Me2-2,6)4(NMe2)] (1). The related reaction between Ti(NEt2)4 and 10 equivalents of ButSH in toluene afforded a mixture of two complexes, [Ti(SBut)4] (3) and [Ti(SBut)3(NEt2)] (4). X-Ray crystal structures of 1 and 4 have been determined. Vapour phase thin-film studies of compounds 1 and 3/4 revealed that 1 is not an effective tantalum sulfide precursor whereas 3/4 produced TiS2.

  Ta(NMe2)5 与 10 等量的 2,6-Me2C6H3SH 在甲苯中反应，生成了[Ta(SC6H3Me2-2,6)4(NMe2)] (1) 的鲜红色晶体。Ti(NEt2)4 和 10 等量的 ButSH 在甲苯中发生了相关反应，生成了[Ti(SBut)4](3) 和[Ti(SBut)3(NEt2)](4) 两种复合物的混合物。1 和 4 的 X 射线晶体结构已经确定。化合物 1 和 3/4 的气相薄膜研究表明，1 不是一种有效的硫化钽前体，而 3/4 则产生了 TiS2。