[Ti(C5H4NC(Me)(CH2NSiMe3)2)(diphenylhydrazido(2-))(pyridine)] | 1085417-57-7

• 英文名称: [Ti(C5H4NC(Me)(CH2NSiMe3)2)(diphenylhydrazido(2-))(pyridine)]
• 英文别名: Ti((2-NC5H4)CMe(CH2NSiMe3)2)(NNPh2)(py)
• CAS: 1085417-57-7
• 化学式: C₃₂H₄₄N₆Si₂Ti
• 分子量: 616.793
• InChiKey: OURNHPOXZPSXSA-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(C5H4NC(Me)(CH2NSiMe3)2)(diphenylhydrazido(2-))(pyridine)] 、 C6F5C2Me 以 苯 为溶剂， 生成 Ti((2-NC5H4)CMe(CH2NSiMe3)2)[N(NPh2)C(Me)C(C6F5)]
  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：

  [TiCl2(diphenylhydrazido(2-))(pyridine)3] 、 Li2((2-NC5H4)C(Me)(CH2NSiMe3)2) 以 甲苯 为溶剂， 以73%的产率得到[Ti(C5H4NC(Me)(CH2NSiMe3)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

• Cycloaddition reactions of transition metal hydrazides with alkynes and heteroalkynes: coupling of TiNNPh2 with PhCCMe, PhCCH, MeCN and tBuCP
  作者：Jonathan D. Selby、Christian Schulten、Andrew D. Schwarz、Andreas Stasch、Eric Clot、Cameron Jones、Philip Mountford

  DOI：10.1039/b813911c

  日期：——

  The first structurally authenticated [2+2] cycloaddition products of any transition metal hydrazide complexes are reported; cycloaddition products of transition metal hydrazides with alkynes and heteroalkynes have been obtained for the first time; these are the first structurally authenticated cycloaddition products for any transition metal MNNR2 functional group.

  报告了首个经过结构验证的[2+2]环加成产物，这些产物来自任何过渡金属肼类配合物；首次获得了过渡金属肼类与炔烃和异炔烃的环加成产物；这些是任何过渡金属MNNR2功能团的首个经过结构验证的环加成产物。
• 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。