[Ti(pentamethylcyclopentadienyl)(N(xylyl)C4H6N)(1-methyl-1-phenylhydrazinediido)(pyridine)] | 1160299-01-3

• 英文名称: [Ti(pentamethylcyclopentadienyl)(N(xylyl)C4H6N)(1-methyl-1-phenylhydrazinediido)(pyridine)]
• 英文别名: [Ti(η5-pentamethylcyclopentadienyl)((Xyl)-2-aminopyrrolinato)(py)(NN(Ph)Me)]；[Ti(C5Me5)(py)(1-methyl-1-phenylhydrazinediido)(N(xylyl)C4H6N)]
• CAS: 1160299-01-3
• 化学式: C₃₄H₄₃N₅Ti
• 分子量: 569.629
• InChiKey: YPMOAKLSPRYIIC-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：

  [Ti(pentamethylcyclopentadienyl)(N(xylyl)C4H6N)(1-methyl-1-phenylhydrazinediido)(pyridine)] 、 N,N'-二异丙基碳二亚胺 以 氘代苯 为溶剂， 反应 0.25h， 生成
  参考文献：
  名称：

  Titanium-Catalyzed Hydrohydrazination of Carbodiimides

  摘要：

  Hydrazinediido complexes of the type [Cp*Ti-(NxylN)(NNR2)(L)] (R = Ph, Me; Ar, fluorene, L = (BuNH2)-Bu-t, Py; 3a-e) have been synthesized and used as catalysts for the hydrohydrazination of a series of carbodiimides, yielding aminoguanidines or fluoreneiminoguanidines. The highest yields were obtained for diarylhydrazines and fluorenone 5 hydrazone at temperatures between 80 and 105 degrees C. Stoichiometric reactions of hydraz inediido complexes with (PrNCNPr)-Pr-i-Pr-i led to an equilibrium with the resulting [2 + 2] cydoadducts 4a-f, which were characterized by H-1, C-13, and N-15 NMR spectroscopy as well as X-ray diffraction. The proposed mechanism, which is closely related to that previously established for the hydrohydrazination of alkynes and allenes, was found to be consistent with the results of a kinetic study. The dynamic structures of aminoguanidines and fluoreneiminoguanidines were characterized by NMR spectroscopy, and the minimum configurations were foud to be stabilized by intramolecular hydrogen bonding.

  DOI：

  10.1021/om400323p
• 作为产物：
  描述：

  吡啶 、 [Ti(pentamethylcyclopentadienyl)(N(xylyl)C4H6N)(tert-butylimido)(tert-butylamine)] 、 1-甲基-1-苯肼 以 正己烷 、 甲苯 为溶剂， 以74%的产率得到[Ti(pentamethylcyclopentadienyl)(N(xylyl)C4H6N)(1-methyl-1-phenylhydrazinediido)(pyridine)]
  参考文献：
  名称：

  肼二钛钛半三明治复合物：高活性催化剂，用于在环境温度下末端炔烃的氢酰化反应

  摘要：

  [Cp * Ti（N Xyl N）（N t Bu）（NH 2 t Bu）]与1摩尔当量的二苯肼反应生成肼二基配合物[Cp * Ti（N Xyl N）（NNPh 2）（NH 2 t Bu）]（1a），而橙色吡啶加合物[Cp * Ti（N Xyl N）（NNPh 2）（py）]（1b）是通过使酰亚胺[Cp * Ti（N Xyl N）（N t在吡啶的存在下，用二苯肼（Bu）（NH 2 t Bu）]。的叔丁基胺配位到金属中心1A通过在60℃和10 -6毫巴下加热固体72小时，可以除去[Cp * Ti（N Xyl N）（NNPh 2）]（1c）。在吡啶或4-二甲基氨基吡啶（dmap）作为中性共配体存在下，肼二基配合物[Cp * Ti（N Xyl N）（NNMePh）（py）]（2a）和[Cp * Ti（N Xyl N）制备了NNMePh）（dmap）]（2b）以及[Cp * Ti（N Xyl N）（NNMe

  DOI：

  10.1021/om900155t

文献信息

• Reactions of Titanium Hydrazinediido Complexes with Unsaturated Organic Substrates
  作者：Katharina Weitershaus、Julio Lloret Fillol、Hubert Wadepohl、Lutz H. Gade

  DOI：10.1021/om900428d

  日期：2009.8.24

  chemical shifts, along with an X-ray diffraction study of 2a, allowed the assignment of the diastereomers as the cycloadducts derived from a (3,2)-cycloaddition of the allene to the Ti═N bond. Upon reaction of 1a with phenylisothiocyanate, two complexes were formed in a 3:1 ratio. The major isomer, [Cp*Ti(NXylN)κ2-N(NPh2)C(NPh)S}] (4a), was isolated and identified by X-ray diffraction to result from a [2+2]

  [Cp * Ti（N Xyl N）N-NPh 2 }（NH 2 t Bu）]（1a）与1摩尔当量的苯丙二烯反应导致形成两种金属环化合物[Cp * Ti（ ñ的Xyl N）κ 2 N（NPH 2）C（CHPh配合）CH 2 }]（图2a和图2b中的3摩尔比）为1:1。比较13 C和15 N NMR共振与计算出的化学位移以及2a的X射线衍射研究，允许将非对映异构体指定为衍生自丙二烯与Ti═N键的（3,2）-环加成的环加合物。1a与苯基异硫氰酸酯反应后，以3：1的比例形成了两种络合物。主要异构体，混合[Cp *的Ti（N的Xyl N）κ 2 -N（NPH 2）C（NPH）S}]（4A），通过X射线衍射分离和鉴定以从[2 + 2导致]在PhNCS中将C═S键与肼二基单元的Ti═N键进行环加成反应，得到一个四元金属环，在钛中心具有S，N配位，并带有一个环外C═N双键。在次要化合物中（4b）在环