[TiCl2(diphenylhydrazido(2-))(pyridine)3] | 1085417-49-7

• 英文名称: [TiCl2(diphenylhydrazido(2-))(pyridine)3]
• 英文别名: Ti(NNPh2)Cl2(pyridine)3
• CAS: 1085417-49-7
• 化学式: C₂₇H₂₅Cl₂N₅Ti
• 分子量: 538.315
• InChiKey: WDUFWEQXYKPIFV-UHFFFAOYSA-L

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：

  [TiCl2(diphenylhydrazido(2-))(pyridine)3] 以 neat (no solvent) 为溶剂， 以99%的产率得到[TiCl₂(diphenylhydrazido^(2-))(pyridine)2]2
  参考文献：
  名称：

  Titanium Hydrazides Supported by Diamide-Amine and Related Ligands: A Combined Experimental and DFT Study

  摘要：

  This paper reports a general method for the synthesis of new terminal titanium diphenyl hydrazido(2-) complexes containing dianionic N-3- and N-4-donor ligands, along with new hydrazido synthons. Reaction of Ti((NBu)-Bu-t)Cl-2(py)(3) or Ti((NBu)-Bu-t)Cl-2(py')(3) (py' = 4-(NC5H4Bu)-Bu-t) with Ph2NNH2 gave excellent yields of the corresponding monomeric hydrazides Ti(NNPh2)Cl-2(L)(3) (L = py (7) or py'), which have been structurally characterized. Application of a dynamic vacuum to 7 formed [Ti(NNPh2)Cl-2(py)(2)](2) (4). Both 4 and 7 are entry points to new titanium hydradizo complexes on reaction with metalated reagents. In this way, four new five-coordinate diamide-amine complexes Ti(NNPh2)("N2N")(py) were made ("N2N" MeN(CH2CH2NSiMe3)(2), Me3SiN(CH2CH2NSiMe3)(2), MeN(CH2CH2CH2NSiMe3)(2), (2-NC5H4)C(Me)(CH2NSiMe3)(2)) and structurally characterized. Five- and six-coordinate terminal titanium hydrazides containing dianionic N-4- or O2N2-donor ligands were also synthesized from 4 by an analogous method. The identity of the "N2N" ligand affects the Ti=N-alpha and N-alpha-N-beta distances of the Ti=N-NPh2 functional group. A detailed DFT analysis of the bonding in these and a range of model complexes is presented using molecular orbital and natural bond orbital methods. The competition between N(amide) and N(hydrazide) Ti(3d(pi))-N(2p(pi)) interactions has an indirect and significant effect on the N-alpha-N-beta bond.

  DOI：

  10.1021/om8007597
• 作为产物：
  描述：

  dichloro tert-butylimido trispyridine titanium(IV) 、 N,N-二苯基肼 以 苯 为溶剂， 以89%的产率得到[TiCl2(diphenylhydrazido(2-))(pyridine)3]
  参考文献：
  名称：

  Titanium Hydrazides Supported by Diamide-Amine and Related Ligands: A Combined Experimental and DFT Study

  摘要：

  This paper reports a general method for the synthesis of new terminal titanium diphenyl hydrazido(2-) complexes containing dianionic N-3- and N-4-donor ligands, along with new hydrazido synthons. Reaction of Ti((NBu)-Bu-t)Cl-2(py)(3) or Ti((NBu)-Bu-t)Cl-2(py')(3) (py' = 4-(NC5H4Bu)-Bu-t) with Ph2NNH2 gave excellent yields of the corresponding monomeric hydrazides Ti(NNPh2)Cl-2(L)(3) (L = py (7) or py'), which have been structurally characterized. Application of a dynamic vacuum to 7 formed [Ti(NNPh2)Cl-2(py)(2)](2) (4). Both 4 and 7 are entry points to new titanium hydradizo complexes on reaction with metalated reagents. In this way, four new five-coordinate diamide-amine complexes Ti(NNPh2)("N2N")(py) were made ("N2N" MeN(CH2CH2NSiMe3)(2), Me3SiN(CH2CH2NSiMe3)(2), MeN(CH2CH2CH2NSiMe3)(2), (2-NC5H4)C(Me)(CH2NSiMe3)(2)) and structurally characterized. Five- and six-coordinate terminal titanium hydrazides containing dianionic N-4- or O2N2-donor ligands were also synthesized from 4 by an analogous method. The identity of the "N2N" ligand affects the Ti=N-alpha and N-alpha-N-beta distances of the Ti=N-NPh2 functional group. A detailed DFT analysis of the bonding in these and a range of model complexes is presented using molecular orbital and natural bond orbital methods. The competition between N(amide) and N(hydrazide) Ti(3d(pi))-N(2p(pi)) interactions has an indirect and significant effect on the N-alpha-N-beta bond.

  DOI：

  10.1021/om8007597

文献信息

• Synthesis, Structures and Reactivity of Group 4 Hydrazido Complexes Supported by Calix[4]arene Ligands
  作者：Andrew J. Clulow、Jonathan D. Selby、Michael G. Cushion、Andrew D. Schwarz、Philip Mountford

  DOI：10.1021/ic801735c

  日期：2008.12.15

  TiCl(2)(Me(2)Calix) with 2 equiv of LiNHNRR' afforded the corresponding terminal hydrazido(2-) complexes Ti(NNRR')(Me(2)Calix) (R = Ph, R' = Ph (1) or Me; R = R' = Me (3)) which were all structurally characterized. The X-ray structure of Ph(2)NNH(2) is reported for comparison. Compound 1 was also prepared from Na(2)[Me(2)Calix] and Ti(NNPh(2))Cl(2)(py)(3). Reaction of ZrCl(2)(Me(2)Calix) with 2 equiv

  TiCl（2）（Me（2）Calix）与2当量的LiNHNRR'反应得到相应的末端hydrazido（2-）配合物Ti（NNRR'）（Me（2）Calix）（R = Ph，R'= Ph （1）或Me； R = R'= Me（3））都在结构上得到了表征。据报道Ph（2）NNH（2）的X射线结构进行比较。还从Na（2）[Me（2）Calix]和Ti（NNPh（2））Cl（2）（py）（3）制备化合物1。ZrCl（2）（Me（2）Calix）与2当量LiNHNR（2）的反应仅提供了bis（hydrazido（1-））复合物Zr（NHNR（2））（2）（Me（2）Calix） （R = Ph或Me）。通过MeI处理Ti（NNMe（2））（Me（2）Calix）（3），通过净异构化反应得到两性离子的水合肼物种Ti（NNMe（3））（MeCalix）（6），该反应被认为具有催化作用在MeI中。3与CD