dichlorotantalum,methanidylbenzene | 59326-13-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dichlorotantalum,methanidylbenzene
• 英文别名: Cl2Ta(CH2Ph)3；TaCl2(CH2Ph)3
• CAS: 59326-13-5
• 化学式: C₂₁H₂₁Cl₂Ta
• 分子量: 525.252
• InChiKey: VDMKOXHLWGDOMR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.58
• 重原子数：
  24.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  Na(silox) 、 dichlorotantalum,methanidylbenzene 以 苯 为溶剂， 生成 tribenzylbis((tri-tert-butylsilyl)oxy)tantalum
  参考文献：
  名称：

  含大量氧供体的有机钽金属：利用三叔丁基氧化硅和9-氧三茂铁

  摘要：

  DOI：

  10.1021/om00129a022
• 作为产物：
  描述：

  五氯化钽 、 dibenzylzinc 以 甲苯 、 正戊烷 为溶剂， 反应 2.0h， 以68%的产率得到dichlorotantalum,methanidylbenzene
  参考文献：
  名称：

  Cycloaddition and C–H Activation Reactions of a Tantalum Alkylidyne

  摘要：

  The alkylidyne complex (C5Me5)Ta(=CPh)(PMe3)(2)Cl (1) was first reported by Schrock in 1978, but little if any follow-up work on 1 or other group 5 metal alkylidynes has been reported. This work discloses two avenues of reactivity of 1. Treatment of 1 with 3-hexyne resulted in the formation of a tantalacyclobutadiene. Abstraction of chloride from 1 led to a mixture of products that included isomers of [(C5Me5)Ta(-CHPh)(CH2PMe2)(PMe3)](+) (4), in which a CH bond of a PMe3 ligand was added across the Ta C bond. The CH activation was found to be reversible, and the equilibrium mixture functioned as an equivalent of a cationic Ta alkylidyne in reaction with 3-hexyne, producing a cationic tantalacyclobutadiene (6). Compounds 4 and 6 were structurally characterized in the solid state by XRD methods, with 6 being the first structurally characterized metallacyclobutadiene in group 5.

  DOI：

  10.1021/acs.organomet.5b00205

文献信息

• Synthesis and Reactivity of Tantalum Complexes Supported by Bidentate X₂ and Tridentate LX₂ Ligands with Two Phenolates Linked to Pyridine, Thiophene, Furan, and Benzene Connectors: Mechanistic Studies of the Formation of a Tantalum Benzylidene and Insertion Chemistry for Tantalum−Carbon Bonds
  作者：Theodor Agapie、Michael W. Day、John E. Bercaw

  DOI：10.1021/om8002653

  日期：2008.12.8

  phosphine coordination to the resulting benzylidene species. An X-ray structure determination reveals that the benzylidene π-bond is oriented perpendicular to the oxygen−oxygen vector, in accord with the prediction of DFT calculations. Tantalum alkyl complexes with the benzene-linked bis(phenolate) ligand (Ta(CH3)2[(OC6H2-tBu2)2C6H3] (16), Ta(CH2Ph)2[(OC6H2-tBu2)2C6H3] (17), and TaCl2CH3[(OC6H2-tBu2)2C6H4]

  使用烷烃消除或盐复分解方法，已使用具有三齿双（酚盐）供体（供体=吡啶，呋喃和噻吩）或双齿双（酚盐）苯的新配体体系制备了钽配合物。配体骨架具有两个X型酚盐，它们通过直接的环环连接到苯的2,6-或2,5-位置上的平面杂环L-型供体或苯的2,6-位置上（sp 2 -sp 2）联系。这些复合物的固态结构表明，在所有情况下，配体均以mer形式结合，但具有不同的LX 2骨架几何形状。吡啶联系统结合在一个Ç小号-时尚，在呋喃联系统Ç2V -时尚，并且在一个噻吩联系统Ç 1 -时尚。当在二甲基苯基膦存在下加热时，双（酚盐）吡啶钽三苄基物种（7）通过α-氢提取而产生稳定的亚苄基络合物，其中甲苯损失并且PMe 2 Ph捕集。该过程被认为是独立的PME 2与Δ博士浓度ħ ⧧ = 31.3±0.6千卡·摩尔-1和Δ小号⧧ = 3±2卡·摩尔-1 ·K -1，和动力学同位素效应ķ ħ / k D＝ 4.9±0.4，
• Synthesis, Reactivity, and DFT Studies of Tantalum Complexes Incorporating Diamido-<i>N</i>-heterocyclic Carbene Ligands. Facile Endocyclic C−H Bond Activation
  作者：Liam P. Spencer、Chad Beddie、Michael B. Hall、Michael D. Fryzuk

  DOI：10.1021/ja063282x

  日期：2006.9.1

  elimination reactions with the diamine-NHC ligands, (Ar)[NCN]H(2) (where (Ar)[NCN]H(2) = (ArNHCH(2)CH(2))(2)(C(3)N(2)); Ar = Mes, p-Tol), provided complexes with a bidentate amide-amine donor configuration. Attempts to promote coordination of the remaining pendent amine donor were unsuccessful. Metathesis reactions with the dilithiated diamido-NHC ligand ((Ar)[NCN]Li(2)) and various Cl(x)Ta(NR'(2))(5-)(x)

  描述了具有潜在三齿二酰氨基-N-杂环卡宾 (NHC) 配体的钽衍生物的合成。与二胺-NHC 配体 (Ar)[NCN]H(2) 的氨解和烷烃消除反应 (其中 (Ar)[NCN]H(2) = (ArNHCH(2)CH(2))(2)(C (3)N(2)); Ar = Mes, p-Tol)，提供具有双齿酰胺-胺供体构型的复合物。促进剩余悬垂胺供体协调的尝试未成功。与二氨基-NHC 配体 ((Ar)[NCN]Li(2)) 和各种 Cl(x)Ta(NR'(2))(5-)(x) 前体的复分解反应成功并生成了所需的八面体(Ar)[NCN]TaCl(x)(NR'(2))(3-)(x) 络合物。通过这种方法制备三烷基钽配合物的尝试导致了不寻常的金属氮丙啶衍生物的形成。对模型配合物的 DFT 计算表明，形成了应变的金属氮丙啶环，因为它允许剩余的取代基采用优选的键合位置。计算预测最低能量途径涉及钽亚烷基中间体，该中间体经历
• WO2008/36882
  申请人：——

  公开号：——

  公开（公告）日：——
• Multiple metal-carbon bonds. 17. Preparation of monocyclopentadienyl benzylidene complexes of tantalum and the crystal structure of Ta(.eta.5-C5Me5)(CHPh)(CH2Ph)2
  作者：L. W. Messerle、P. Jennische、R. R. Schrock、G. Stucky

  DOI：10.1021/ja00542a013

  日期：1980.10
• Conversion of Alkyltantalum Chlorides to Fluorides Using Trimethyltin Fluoride as a Fluorinating Agent. Crystal Structures of (<i>p</i>-MeC₆H₄CH₂)₃TaF₂, (Me₃SnCl·Me₃SnF·TaF₅)<i>_n</i>, (Me₃Si)₂CHTaCl₄, {(Me₃Si)₂CHTaCl₄·[(Me₃Si)₂CH]₂Ta₂Cl₆(μ₂-O)}, and (Me₃Si)₂CHTaF₄
  作者：Olexandr I. Guzyr、Mark Schormann、Jürgen Schimkowiak、Herbert W. Roesky、Christopher Lehmann、Mrinalini G. Walawalkar、Ramaswamy Murugavel、Hans-Georg Schmidt、Mathias Noltemeyer

  DOI：10.1021/om980768g

  日期：1999.3.1

  The reactions of alkyltantalum chlorides with trimethyltin fluoride were found to be highly dependent on the number of organic ligands on tantalum as well as on the electronic and the steric nature of the substituents. The synthesis of trialkyltantalum difluorides of general formula (RCH2)(3)TaF2 (R = Ph, 1; R = p-Tol, 2; R = Me3Si, 3) and the first example of the alkyltantalum tetrafluoride (Me3Si)(2)CHTaF4 (8) are reported. The compounds (p-MeC6H4CH2)(3)TaF2, (Me3SnCl . Me3SnF . TaF5)(n), (Me3Si)(2)CHTaCl4, (Me3Si)(2)CHTaCl4.[(Me3Si)(2)CH](2)Ta(2)Cl6(mu(2)-O)}, and (Me3Si)(2)CHTaF4 respectively have been characterized by single-crystal X-ray structural analysis.