[Ti(MeN(CH2CH2NSiMe3)2)(diphenylhydrazido(2-))(pyridine)] | 1006654-58-5

• 英文名称: [Ti(MeN(CH2CH2NSiMe3)2)(diphenylhydrazido(2-))(pyridine)]
• 英文别名: Ti(MeN(CH2CH2NSiMe3)2)(NNPh2)(py)；Ti(MeN(CH2CH2NSiMe3)2)[NNPh2](py)
• CAS: 1006654-58-5
• 化学式: C₂₈H₄₄N₆Si₂Ti
• 分子量: 568.749
• InChiKey: CJFZZBWWRJPOAU-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(MeN(CH2CH2NSiMe3)2)(diphenylhydrazido(2-))(pyridine)] 、 1-(tert-butyl)-4-(prop-1-yn-1-yl)benzene 以 乙醚 为溶剂， 生成 Ti(MeN(CH2CH2NSiMe3)2)[NC(4-C6H4(t)Bu)C(Me)NPh2](py)
  参考文献：
  名称：

  M=Nα环加成和Nα-Nβ插入钛酰肼化合物与炔烃的反应：联合实验和计算研究

  摘要：

  提出了二酰胺-胺负载的钛酰肼与炔烃反应的联合实验和 DFT 研究。Ti(N2N(py))(NNPh2)(py) (1, N2N(py) = (2-NC5H4)CMe(CH2NSiMe3)2) 与末端和内部芳基炔烃 ArCCR（Ar = Ph 或取代苯基，R = Me 或 H) 在室温下通过 ArCCR [2 + 2] 环加成到 Ti=N(alpha) 键，得到完全验证的氮杂钛烷环丁烯 Ti(N2N(py)){N(NPh2)C(R)CAr}酰肼配体。相比之下，1 与 PhCCMe 在 60 摄氏度，或 Ti(N2NMe)(NNPh2)(py) (11, N2NMe = MeN(CH2CH2NSiMe3)2) 与 RCCMe（R = Me，Ph 或取代苯基）在室温下的反应温度或以下，得到 Ti(N2N(R')){NC(R)C(Me)NPh2}(py) 类型的乙烯基亚胺化合物，其中 RCCMe 已净插入

  DOI：

  10.1021/ja1036513
• 作为产物：
  描述：

  dilithium salt of N-methyl-N',N''-bis(trimethylsilyl)diethylenetriamine 、 [TiCl2(diphenylhydrazido(2-))(pyridine)3] 以 甲苯 为溶剂， 以65%的产率得到[Ti(MeN(CH2CH2NSiMe3)2)(diphenylhydrazido(2-))(pyridine)]
  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

• New ligand platforms for developing the chemistry of the TiN–NR2 functional group and the insertion of alkynes into the N–N bond of a TiN–NPh2 ligand
  作者：Jonathan D. Selby、Catherine D. Manley、Marta Feliz、Andrew D. Schwarz、Eric Clot、Philip Mountford

  DOI：10.1039/b711941k

  日期：——

  Two broadly applicable strategies for extending the available ligand platforms of the virtually unexplored terminal TiN–NR2 functional group are described, along with the highly selective room temperature insertion of alkynes into the N–N bond of TiMeN(CH2CH2NSiMe3)2}(NNPh2)(py) and the catalytic cis-diamination of PhCCMe by diphenylhydrazine.

  本文介绍了两种广泛适用的策略，以扩展几乎尚未开发的末端 TiNâNR2 官能团的可用配体平台，以及在室温下将炔烃高选择性地插入 TiMeN(CH2CH2NSiMe3)2}(NNPh2)(py) 的 NâN 键和二苯肼催化 PhCCMe 顺二歧化。
• Single and double substrate insertion into the TiN_αbonds of terminal titanium hydrazides
  作者：Pei-Jen Tiong、A. Daniel Schofield、Jonathan D. Selby、Ainara Nova、Eric Clot、Philip Mountford

  DOI：10.1039/b920090h

  日期：——

  Nitriles, CO(2) and isocyanates undergo net single or double insertion reactions into the Ti=N(alpha) multiple bonds of terminal titanium hydrazides. These are the first such examples of this type of reactivity for any transition metal hydrazide complex.

  腈，CO（2）和异氰酸酯经历净单或双插入反应到末端钛酰肼的Ti =Nα多键中。这些是对于任何过渡金属酰肼配合物这类反应性的第一个此类实例。