tetrakis(dimethylamino)tantalum chloride | 1092381-62-8

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: tetrakis(dimethylamino)tantalum chloride
• 英文别名: TaCl(N(methyl)₂)₄；TaCl(dimethylamide)4；(Me2N)4TaCl；TaCl(NMe2)4；dimethylazanide;tantalum(5+);chloride
• CAS: 1092381-62-8；82482-88-0
• 化学式: C₈H₂₄ClN₄Ta
• 分子量: 392.706
• InChiKey: BDCVDNDSINALTK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.52
• 重原子数：
  14
• 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：
  4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tetrakis(dimethylamino)tantalum chloride 、 异丙基锂 以 正己烷 为溶剂， 以80%的产率得到tetrakis(dimethylamino)(isopropyl)tantalum
  参考文献：
  名称：

  Crystal and molecular structures of tert-butyltetrakis(dimethylamido)tantalum(V), bromo(p-tolyl)tris(dimethylamido)tantalum(V), and [(trimethylsilyl)methyl]tetrakis(N,N-dimethylcarbamato)tantalum(V). Evidence for stabilization of .sigma.-alkyl ligands by strongly .pi.-donating ligands in early transition metal chemistry

  摘要：

  DOI：

  10.1021/ja00382a022
• 作为产物：
  描述：

  三甲基氯硅烷 、 五(二甲氨基)钽(V) 生成 tetrakis(dimethylamino)tantalum chloride
  参考文献：
  名称：

  Allyl Ligand Reactivity in Tantalum(V) Compounds: Experimental and Computational Evidence for Allyl Transfer to the Formamidinate Ligand in fac-Ta(NMe₂)₃(η¹-allyl)[ⁱPrNC(H)NⁱPr] via a Metallo-Claisen Rearrangement

  摘要：

  Treatment of TaCl(NMe2)(4) (1) with allylMgCl furnishes the allyl-substituted compound Ta(NMe2)(4)(eta(1)-allyl) (2) in moderate yield. The X-ray structure of 2 reveals a trigonal-bipyramidal geometry at the tantalum center with an equatorially situated eta(1)-allyl moiety. VT H-1 NMR measurements confirm that the molecule is fluxional in solution over the temperature range 298-193 K, and DFT calculations indicate that the time-averaged environment exhibited 1:1 the allyl moiety in fluid solution derives from a rapid eta(1)-to-eta(3) equilibration, with Ta(NMe2)(4)(eta(3)-allyl) serving as the transition state for this process. 1 reacts rapidly with the formarnidine (PrNC)-Pr-i-(H)(NHPr)-Pr-i to yield fac-TaCl(NMe2)(3)[(PrNC)-Pr-i(H)(NPr)-Pr-i] (5) and Me2NH, and the tantalum product has been characterized by NMR spectroscopy and X-ray diffraction analysis. The five-coordinate compound Ta(NMe2)(3)[(PrNCH)-Pr-i(allyl)(NPr)-Pr-i] (7), whose origin is traced to the putative octahedral species fac-Ta(NMe2)(3)(eta(1)-allyl) [(PrNC)-Pr-i(H)(NPr)-Pr-i] (6), has been obtained from the reaction of 2 with (PrNC)-Pr-i(H)(NHPr)-Pr-i; 7 may also be prepared from the reaction of 5 with allylMgCl. The rearrangement of the allyl moiety in fac-Ta(NMe2)(3)(eta(1)-allyl)[(PrNC)-Pr-i(H)(NPr)-Pr-i] to the formamidinate carbon atom in 7 has been investigated by DFT calculations. Here the DFT calculations have provided crucial insight into the reaction mechanism and the composition of those transient species that do not lend themselves to direct spectroscopic observation. The computed barrier for this metallo-Claisen rearrangement is sensitive to the nature of the density functional employed, and the barrier computed using the meta-GGA TPSS functional provides the best agreement with the experimental conditions. The related alkenyl derivatives Ta(NMe2)(4)(eta(1)-3-butenyl) (3) and Ta(NMe2)(3)(eta(1)-3-butenyl)[(PrNC)-Pr-i(H)(NPr)-Pr-i] (8) have been synthesized, and their reactivity is contrasted with the corresponding allyl-substituted analogues.

  DOI：

  10.1021/om200683q

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
• Crystal Structure of TaCl(NMe₂)₄ and Its Reactions with Lithium Amides and Water. Indirect Observation of an Equilibrium among TaCl(NMe₂)₄, Ta(NMe₂)₅ and Ta₂(μ-Cl)₂(NMe₂)₆Cl₂
  作者：Shu-Jian Chen、Hu Cai、Zi-Ling Xue

  DOI：10.1021/om800362t

  日期：2009.1.12

  Reactions of TaCl(NMe2)4 (2) with LiNR2 (R = SiMe3, Et), yielding Ta(NMe2)4(NR2) (R = SiMe3, 4; Et, 7), Ta(NMe2)5 (1), (Me2N)3TaN(SiMe3)SiMe2CH2 (5), and Ta(NMe2)3(NEt2)2 (8), respectively, suggest the presence of an equilibrium among TaCl(NMe2)4 (2), Ta(NMe2)5 (1), and Ta2(μ-Cl)2(NMe2)6Cl2 (3): 2 2 ⇌ 1 + 0.5 3. New products Ta(NMe2)4(NR2) have been characterized. Ta(NMe2)4(NEt2) (7), Ta(NMe2)5 (1)

  TACL的反应（NME 2）4（2）与LINR 2（R =森达3，等），产生的TA（NME 2）4（NR 2）（R =森达3，4 ;内皮素，7），钽（NME 2）5（1），（Me 2 N）3 TAN（SiMe 3）SiMe 2 CH 2（5）和TA（NMe 2）3（NEt 2）2（8）分别表明TACl（NMe 2）4（2），TA（NMe 2）5（1）和TA 2（μ-Cl）2（NMe 2）6 Cl 2（3）之间存在平衡：2 2 1 + 0.5 3。已经表征了新产品TA（NMe 2）4（NR 2）。TA（NMe 2）4（NEt 2）（7），TA（NMe 2）5（1）和TA（NMe 2）3（NEt 2）2（8）处于缓慢交换中：2 7⇌1 + 8在90°C下的平衡常数为K eq = 0.25（0.01）。还报道了以下内容：X射线晶体结构和TACl（NMe 2）4（2）的一步合成，2与H 2 O反应生成TA
• Guanidinate anions and dianions. Reactions involving alkylguanidines, (RNH)2CNR (R = i-Pr or Cy), and metal amido complexes M(NMe2)5 (M = Ta or Nb)
  作者：Ma K. T. Tin、Natesan Thirupathi、Glenn P. A. Yap、Darrin S. Richeson

  DOI：10.1039/a904072b

  日期：——

  Protonation of the amido groups of M(NMe2)5 (M = Ta or Nb) with trialkylguanidines, (RNH)2CNR (R = i-Pr or Cy), directly produced a series of five-co-ordinated complexes, M(NMe2)3[(RN)2CNR] 1–4. Single crystal X-ray analysis confirmed that 1 contained a dianionic N,N′,N″-triisopropylguanidinate ligand which was co-ordinated in a chelating bidentate mode. In contrast, protonation of the amido groups of Ta(NMe2)4Cl with triisopropylguanidine gave the six-co-ordinated complex Ta(NMe2)3Cl[(i-PrN)2CNHi-Pr] 5 which possessed a bidentate monoanionic guanidinate ligand. Complex 5 can be converted into 1 by reaction with either LiNMe2 or MeMgBr.

  M(NMe2)5（M = Ta 或 Nb）中酰胺基团的质子化与三烷基胍（(RNH)2CNR，R = i-Pr 或 Cy）直接生成了一系列五配位络合物 M(NMe2)3[(RN)2CNR] 1–4。单晶X射线分析证实，化合物 1 具有一种二阴离子 N,N′,N″-三异丙基胍酸盐配体，以螯合二齿的方式配位。相比之下，Ta(NMe2)4Cl 中酰胺基团的质子化与三异丙基胍反应生成了六配位络合物 Ta(NMe2)3Cl[(i-PrN)2CNHi-Pr] 5，该络合物具有一个二齿单阴离子胍酸盐配体。络合物 5 可以通过与 LiNMe2 或 MeMgBr 反应转化为 1。
• 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