(Me2N)3TaCl2 | 224638-03-3

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: (Me2N)3TaCl2
• 英文别名: TaCl2(NMe2)3；TaCl2(dimethylamide)3；dimethylazanide;tantalum(5+);dichloride
• CAS: 224638-03-3
• 化学式: C₆H₁₈Cl₂N₃Ta
• 分子量: 384.083
• InChiKey: CJUQMCMCANTTQH-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.41
• 重原子数：
  12
• 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：
  3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tris(tetrahydrofuran)lithium tris(trimethylsilyl)silanide 、 (Me2N)3TaCl2 以 正戊烷 为溶剂， 以29%的产率得到(Me2N)3Ta[Si(SiMe3)3]2
  参考文献：
  名称：

  锆，Ha和钽的二甲硅烷基络合物。它们的合成，表征和与硅烷基阴离子的交换

  摘要：

  不含环戊二烯基的二甲硅烷基酰胺络合物[（Me 2 N）3 M（SiBu t Ph 2）2 ] -（M = Zr，1 ; Hf，2 as [Li（THF）4 ] +盐），K（18-冠-6）3/2 {（Me 2 N）3 M [（Me 3 Si）2 Si-（CH 2）2 -Si（SiMe 3）2 ]}（M = Zr，3 ; Hf，4），（ Me 2 N）3 Ta [Si（SiMe 3）3] 2（5），（Me 2 N）3 Ta（SiBu t Ph 2）2（6）和（Me 2 N）3 Ta（SiBu t Ph 2）[Si（SiMe 3）3 ]（7）具有准备好了。的结构1 - 4已通过X射线单晶衍射确定。两个-Si（森达3）3 -中（ME配体2 N）3的Ta [硅（森达3）3 ]2（5）是由依次-SiBu替换吨博士2 -阴离子，得到（ME 2 N）3 TA（西布吨博士2）[SI（森达3）3 ]（7）和（ME

  DOI：

  10.1021/om050302f
• 作为产物：
  描述：

  tetrakis(dimethylamino)tantalum chloride 、 N-lithio-N-trimethylsilyl-N',N'-dimethylhydrazine 以 正戊烷 为溶剂， 生成 [TaCl2(dimethylamide)3]2 、 (Me2N)3TaCl2 、 Ta(dimethylamide)4(1,1-dimethyl-2-(trimethylsilyl)hydrazide) 、 TaCl(dimethylamide)3(1,1-dimethyl-2-(trimethylsilyl)hydrazide) 、 五(二甲氨基)钽(V)
  参考文献：
  名称：

  New octahedral Ta(V) hydrazido-substituted compounds for atomic layer deposition: Syntheses, X-ray diffraction structures of TaCl(NMe2)3[N(TMS)NMe2] and Ta(NMe2)4[N(TMS)NMe2], and fluxional behavior of the amido and hydrazido ligands in solution

  摘要：

  The synthesis and structural characterization of new tantalum(V) compounds containing a single hydrazido(1) ligand are reported. Hydrazinolysis of TaCl(NMe2)(4) using trimethylsilyl(dimethyl)hydrazine affords the compound TaCl(NMe2)(3)[N(TMS)NMe2] in essentially quantitative yield. Metathetical replacement of the chloride ligand in TaCl(NMe2)(3)]N(TMS)NMe2] by LiNMe2 gives the all-nitrogen coordinated compound Ta(NMe2)(4)[N(TMS)NMe2]. VT H-1 NMR studies support the existence of low-energy pathways involving rotation about the Ta-N bonds of the ancillary amido and hydrazido ligands in both hydrazido-substituted compounds. X-ray crystallographic analyses confirm the octahedral disposition about the tantalum metal in TaCl(NMe2)(3)[N(TMS)NMe2] and Ta(NMe2)(4)[N(TMS)NMe2] and the presence of an mu(2)-hydrazido(1) ligand. Preliminary data using Ta(NMe2)(4)[N(TMS)NMe2] as an ALD precursor for the preparation of tantalum nitride and tantalum oxide thin films are presented. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2010.02.022

文献信息

• [EN] GROUP 5 METAL COMPLEXES USEFUL FOR AMINE FUNCTIONALIZATION AND SYNTHETIC PROCESS FOR MANUFACTURE THEREOF<br/>[FR] COMPLEXES DE MÉTAUX DU GROUPE 5 UTILES POUR LA FONCTIONNALISATION PAR AMINE ET PROCÉDÉ DE SYNTHÈSE POUR LEUR FABRICATION
  申请人：UNIV BRITISH COLUMBIA

  公开号：WO2012040853A1

  公开（公告）日：2012-04-05

  The present invention provides Group 5 metal complexes useful for amine functionalization and synthetic process for manufacture thereof. Provided in this application are halo group 5 metal-amidate complexes having the structure of Formula I: I wherein: M is a group 5 metal, such as Ta, Nb or V; X is a halo substituent, such as CI, F, I or Br; n = 1 or 2,; s = 1 or 2; R1 and R2 are each independently H; a C1 - C25 substituted or unsubstituted, linear, branched or cyclic alkyl; or substituted or unsubstituted aryl or heterocyclic groups; R' is independently a C1 - C25 substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; a substituted or unsubstituted heterocyclic group; or NR32; and each R3 is independently a C1 - C25 substituted or unsubstituted, linear, branched or cyclic alkyl; a substituted or unsubstituted aryl; or substituted or unsubstituted heterocyclic group, and a process for synthesis thereof. Also provided are the corresponding metallaaziridine complexes. The metal complex of Formula I, and the corresponding metallaaziridine complex are useful as a catalysts in ct-alkylation of secondary amines and, therefore, also provided are methods of using the metal complex of Formula I, and the corresponding metallaaziridine complex in o-alkylation of secondary amines. This application also provides methods of using the corresponding non-halo group 5 metal-amidate complexes and metallaaziridine complexes in α-alkylation of heterocycles.

  本发明提供了用于胺官能化的五族金属配合物以及其制造的合成方法。本申请提供了具有以下结构的卤素五族金属酰胺配合物，其结构如公式I所示：其中：M为五族金属，如Ta、Nb或V；X为卤素取代基，如Cl、F、I或Br；n = 1或2；s = 1或2；R1和R2各自独立为H；为C1 - C25取代或未取代的线性、支链或环烷基；或取代或未取代的芳基或杂环基；R'独立为C1 - C25取代或未取代的线性、支链或环烷基；取代或未取代的芳基；取代或未取代的杂环基；或NR32；每个R3独立为C1 - C25取代或未取代的线性、支链或环烷基；取代或未取代的芳基；或取代或未取代的杂环基，以及其合成方法。还提供了相应的金属氮杂环丙烷配合物。公式I的金属配合物和相应的金属氮杂环丙烷配合物在次烷胺的α-烷基化中作为催化剂是有用的，因此，还提供了使用公式I的金属配合物和相应的金属氮杂环丙烷配合物在次烷胺的o-烷基化中的方法。本申请还提供了使用相应的非卤素五族金属酰胺配合物和金属氮杂环丙烷配合物在杂环的α-烷基化中的方法。
• Synthesis of Tantalum(V) Amido Silyl Complexes and the Unexpected Formation of (Me₂N)₃Ta(<i>η</i>²-ONMe₂)[OSi(SiMe₃)₃] from the Reaction of (Me₂N)₄Ta[Si(SiMe₃)₃] with O₂
  作者：Zhongzhi Wu、Hu Cai、Xianghua Yu、Jaime R. Blanton、Jonathan B. Diminnie、Hong-Jun Pan、Ziling Xue、Jeffrey C. Bryan

  DOI：10.1021/om020537g

  日期：2002.9.1

  The synthesis and characterization of amido silyl complexes of tantalum(V) free of π-anionic ligands are reported. The amido silyl chloride complexes (Me2N)3Ta(SiR3)Cl [SiR3 = Si(SiMe3)3 (1a), SiPh2But (2)] were prepared from (Me2N)3TaCl2 and the corresponding silyllithium reagents Li(THF)3Si(SiMe3)3 and Li(THF)3SiPh2But. The amido silyl complexes (Me2N)4Ta(SiR3) [SiR3 = Si(SiMe3)3 (3), SiPh2But (4)]

  报道了无π-阴离子配体的钽（V）酰胺基甲硅烷基配合物的合成和表征。由（Me 2 N）3 TACl 2制备酰胺基甲硅烷基氯络合物（Me 2 N）3 TA（SiR 3）Cl [SiR 3 = Si（SiMe 3）3（1a），SiPh 2 Bu t（2）]。以及相应的甲硅烷基锂试剂Li（THF）3 Si（SiMe 3）3和Li（THF）3 SiPh 2 Bu t。酰胺基甲硅烷基络合物（Me通过（Me 2 N）4 TACl与Li（THF）3的反应合成2 N）4 TA（SiR 3）[SiR 3 = Si（SiMe 3）3（3），SiPh 2 Bu t（4）] SiR 3。复杂3被发现与1个当量的O反应2得到的氧化产物（ME 2 N）3 TA（η 2 -ONMe 2）[OSI（森达3）3 ]（5），并通过X射线晶体学确认5的结构。光谱数据和晶体结构测定表明，围绕TA金属配位几何形状在图1A和2 - 4
• Reaction of Ta(NMe₂)₅ with O₂:  Formation of Aminoxy and Unusual (Aminomethyl)amide Oxo Complexes and Theoretical Studies of the Mechanistic Pathways
  作者：Shu-Jian Chen、Xin-Hao Zhang、Xianghua Yu、He Qiu、Glenn P. A. Yap、Ilia A. Guzei、Zhenyang Lin、Yun-Dong Wu、Zi-Ling Xue

  DOI：10.1021/ja075076a

  日期：2007.11.1

  (Me2N)3Ta(eta2-ONMe2)2 (3) in its reaction with O2. In addition, the reaction of Ta(NMe2)5 with 3 gives 2 only at elevated temperatures. Density functional theory (DFT) calculations have been used to investigate the mechanistic pathways in the reactions of Ta(NMe2)5 (1) with triplet O2. Monomeric reaction pathways in the formation of 2-5 are proposed. A key step is the oxygen insertion into a Ta-N bond in

  d0 Ta(NMe2)5 (1) 与 O2 反应生成两种氨氧基配合物 (Me2N)(n)Ta(eta2-ONMe2)(5-n) (n = 4, 2; 3, 3) 以及 (Me2N )4Ta2[eta2-N(Me)CH2NMe2]2(mu-O)2 (4) 和 (Me2N)6Ta3[eta2-N(Me)CH2NMe2]2(eta2-ONMe2)(mu-O)3 (5)含有新型螯合（氨甲基）酰胺-N（Me）CH2NMe2配体。2-5 的晶体结构已通过 X 射线晶体学确定。(Me2N)4Ta(eta2-ONMe2) (2) 在与 O2 的反应中转化为 (Me2N)3Ta(eta2-ONMe2)2 (3)。此外，Ta(NMe2)5 与 3 的反应仅在升高的温度下产生 2。密度泛函理论 (DFT) 计算已用于研究 Ta(NMe2)5 (1) 与三线态 O2 反应的机理途径。提出了形成 2-5 的单体反应
• Synthesis and characterization of tantalum(V) metallaheterocycle (Me₂N)₃ and chloro-mixed-amide (Me₂N)₃Ta(Cl)[N(SiMe₃)₂]
  作者：Hu Cai、Xianghua Yu、Tianniu Chen、Xue-Tai Chen、Xiao-Zeng You、Ziling Xue

  DOI：10.1139/v03-140

  日期：2003.11.1

  A new mixed-amido complex (Me2N)3Ta(Cl)[N(SiMe3)2] (1) was prepared from the reaction of (Me2N)3TaCl2 with 1 equiv. of LiN(SiMe3)2. The reactions of 1 with 1 equiv. of LiN(SiMe3)2 or (Me2N)3TaCl2 with 2 equiv. of LiN(SiMe3)2 gave (Me2N)3 (2) with a four-membered metallaheterocyclic ring through γ-hydrogen abstraction. In the solid state, 1 adopts a distorted trigonal bipyramidal geometry with the -N(SiMe3)2

  一种新的混合酰胺络合物 (Me2N)3Ta(Cl)[N(SiMe3)2] (1) 是由 (Me2N)3TaCl2 与 1 当量的反应制备的。LiN(SiMe3)2。1与1当量的反应。LiN(SiMe3)2 或 (Me2N)3TaCl2 与 2 当量。LiN(SiMe3)2 通过 γ-氢提取得到具有四元金属杂环的 (Me2N)3 (2)。在固态下，1 采用扭曲的三角双锥几何，-N(SiMe3)2 和-Cl 配体分别位于赤道和轴向位置。2的X射线结构表明它是一个扭曲的三角双锥几何形状，具有平面金属杂环。关键词：钽，γ-氢提取，CH活化，酰胺配合物，金属环。
• Tantalum–Polyhedral Oligosilsesquioxane Complexes as Structural Models and Functional Catalysts for Epoxidation
  作者：Pascal Guillo、Michael I. Lipschutz、Meg E. Fasulo、T. Don Tilley

  DOI：10.1021/acscatal.7b00020

  日期：2017.4.7

  Tantalum-based supported catalysts have been shown to be very selective for epoxidations with aqueous hydrogen peroxide. To gain information relative to the active site on the surface, access to molecular complexes that mimic the active site of the catalyst on the surface is of great interest. In this contribution, several new Ta-polyhedral oligosilsesquioxane (POSS) complexes with POSS ligands are

  钽基负载型催化剂对用过氧化氢水溶液进行环氧化具有很高的选择性。为了获得相对于表面上活性位点的信息，对模拟表面上催化剂活性位点的分子配合物的访问非常感兴趣。在此贡献中，几种具有POSS配体的新型Ta多面体低聚倍半硅氧烷（POSS）配合物用于模拟与二氧化硅结合的Ta位点，并显示出作为环氧化催化剂的活性。值得注意的是，观察到由锗烷氧基配体修饰并具有双核Ta（μ-O）（μ-OH）Ta核的Ta-POSS络合物对于使用过氧化氢水溶液进行环辛烯的环氧化非常有效。