tris(neopentyl)neopentylidenetantalum | 54294-45-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡金属化合物
• 英文名称: tris(neopentyl)neopentylidenetantalum
• 英文别名: [Ta(CHtBu)(CH₂tBu)₃]；Trineopentyl(neopentyliden)tantal；{(Tert.-butylCH2)3Ta(CHtert.-butyl)}；trineopentyl-neopentylidene-tantalum；tantalum tris(neopentyl)-neopentylidene
• CAS: 54294-45-0
• 化学式: C₂₀H₄₃Ta
• 分子量: 464.509
• InChiKey: KXVMNGRZQUBFEZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.34
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tris(neopentyl)neopentylidenetantalum 在 盐酸 作用下， 以 乙醚 为溶剂， 生成 TaCl(CH2tBu)4
  参考文献：
  名称：

  Li, Liting; Hung, Meiling; Xue, Ziling, Journal of the American Chemical Society, 1995, vol. 117, # 51, p. 12746 - 12750

  摘要：

  DOI：
• 作为产物：
  描述：

  Penta(neopentyl)tantalum(v) 以 氘代甲苯 为溶剂， 生成 tris(neopentyl)neopentylidenetantalum
  参考文献：
  名称：

  Abbott, Julia K. C.; Li, Liting; Xue, Zi-Ling, Journal of the American Chemical Society, 2009, vol. 131, p. 8246 - 8251

  摘要：

  DOI：
• 作为试剂：
  描述：

  乙烷 在 silica gel 、 tris(neopentyl)neopentylidenetantalum 作用下， 生成 丙烷 、 异丁烷 、 丁烷 、 methane
  参考文献：
  名称：

  σ-Bond Metathesis of Alkanes on a Silica-Supported Tantalum(V) Alkyl Alkylidene Complex: First Evidence for Alkane Cross-Metathesis

  摘要：

  C-C activation of unactivated alkanes on a silica-supported neopentyl neopentylidene TaV complex [Eq. (1)] affords the alkane cross-metathesis products tBuCH2 R and an alkane-metathesis catalyst. Since the activity and product distributions are similar to those obtained with a silica-supported TaIII hydride, these results are a first step in understanding alkane σ-bond metathesis on metal hydrides.

  DOI：

  10.1002/1521-3773(20010618)40:12<2331::aid-anie2331>3.0.co;2-p

文献信息

• Alkyl, Alkylidene, and Alkylidyne Complexes of Osmium(VI)
  作者：Anne M. LaPointe、Richard R. Schrock、William M. Davis

  DOI：10.1021/ja00122a010

  日期：1995.5

  Addition of dialkylzinc reagents to [PPh&[OsO2C~] gives Os02R2 complexes (R = neopentyl, neophyl, or (trimethylsily1)methyl). The reaction between Os02(CH2-bBu)2 and 2 equiv of Ta(CH-t-Bu)(CHz-t-Bu)3 gave syn,anti-Os(CH-t-Bu)2(CH2-t-B~)2, while [0sOz(CH~SiMe3)2],, reacted to give a 1: 1 mixture of syn,anti-Os(CH-tBu)~(CH2SiMe3)2 and anti,anti-Os(CH-t-Bu)2(CH2SiMe3)2. Isolated anti,anti-Os(CH-t-B~)2(CH2SiMe3)2

  将二烷基锌试剂添加到 [PPh&[OsO2C~] 中得到 OsO2R2 复合物（R = 新戊基、neophyl 或（三甲基甲硅烷基）甲基）。OsO2(CH2-bBu)2 与 2 当量的 Ta(CH-t-Bu)(CH-t-Bu)3 之间的反应得到了合成、反 Os(CH-t-Bu)2( -tB~) 2，而[0sOz(CH~SiMe3)2]，反应得到1:1的syn,anti-Os(CH-tBu)~( SiMe3)2和anti,anti-Os(CH-t-Bu)混合物)2( SiMe3)2。孤立的抗、抗 Os(CH-tB~)2( SiMe3)2 在 X 射线研究中显示为扭曲的四面体，其中两个新戊叉配体位于同一平面。对 Os( )2(CH3)2 进行的扩展 Huckel 计算表明，HOMO 是一个主要为 d,2 特征的轨道，位于 OsC2 碎片平面之间和平面内，LUMO 是 bis(亚甲基），HOMO-1
• [EN] PROCESS FOR MANUFACTURING ALKANES<br/>[FR] PROCEDE DE FABRICATION D'ALCANES
  申请人：BP CHEM INT LTD

  公开号：WO2003104172A1

  公开（公告）日：2003-12-18

  The present invention relates to a process for the manufacture of alkanes comprising an operation in which at least one starting alkane is contacted with a metal catalyst comprising at least one metal, Me, bonded to at least one hydrogen atom and/or to at least one hydrocarbon radical, characterized in that the catalyst is contacted with an agent which forms hydrogen "insitu", during the manufacture of alkanes. The present invention also relates to a process for the activation of a metal catalyst intended to manufacture alkanes and comprising at least one metal, Me, bonded to at least one hydrogen atom and/or to at least one hydrocarbon radical, which process is characterized in that, during the manufacture of alkanes carried out by contacting the catalyst with at least one starting alkane, the catalyst is contacted with an agent which forms hydrogen "in situ". The agent can be chosen from agents capable of releasing hydrogen, preferably by a physical action, and from agents capable of forming hydrogen by a chemical reaction, in particular in the presence of the metal catalyst. The metal Me of the catalyst can be chosen from the lanthanides, the actinides and the metals from Groups 2 to 12, preferably the transition metals from Groups 3 to 11 of the Periodic Table of the Elements. The metal catalyst can be preferably chosen from metal catalysts supported on and in particular grafted to a solid support.

  本发明涉及一种用于制备烷烃的工艺，其中包括将至少一种起始烷烃与至少一种金属催化剂接触，所述金属催化剂包括至少一种金属Me与至少一个氢原子和/或至少一个碳氢基团结合，其特征在于在制备烷烃过程中，将催化剂与一种形成氢的试剂接触。本发明还涉及一种用于激活金属催化剂以制备烷烃的工艺，所述金属催化剂包括至少一种金属Me与至少一个氢原子和/或至少一个碳氢基团结合，其特征在于，在通过将催化剂与至少一种起始烷烃接触进行的烷烃制备过程中，将催化剂与一种形成氢的试剂接触。该试剂可选择自能够通过物理作用释放氢的试剂，以及能够在金属催化剂存在的情况下通过化学反应形成氢的试剂。催化剂的金属Me可选择自镧系元素、锕系元素和元素周期表第2至12族的金属，优选为元素周期表第3至11族的过渡金属。金属催化剂可优选选择自支持在固体支撑上并特别是嫁接到固体支撑上的金属催化剂。
• [EN] PROCESS FOR CONVERTING METHANE INTO ETHANE<br/>[FR] PROCEDE DE CONVERSION DU METHANE EN ETHANE
  申请人：BP CHEM INT LTD

  公开号：WO2003104171A1

  公开（公告）日：2003-12-18

  The invention relates to a process for producing ethane comprising contacting methane with a metal catalyst selected from metal hydrides, metal organic compounds and mixtures thereof. It also relates to a process for the conversion of methane to carbon-containing products comprising contacting methane with a metal catalyst comprising at least one metal, Me, chosen from the lanthanides, the actinides and the metals from Groups 2 to 12 of the Periodic Table of the Elements, so as to produce ethane in a proportion of at least 65%, especially at least 98% or 99% by weight with respect to carbon-containing products formed in the process. The process can be a single-step process, preferably carried out under conditions involving a non-oxidative catalytic coupling of methane, in particular under operating conditions maintained substantially constant, preferably continuously, during the ethane production, e.g. at a temperature ranging from - 30°C to +80°C, preferably from 20°C to 500°C, under a total absolute pressure ranging from 10-3 to 100 MPa, preferably from 0.1 to 50 MPa. The metal catalyst may be chosen from metal catalysts supported on and preferably grafted to a solid support. One of the main advantages of the present invention is to produce ethane with a very high selectivity.

  该发明涉及一种生产乙烷的方法，包括将甲烷与从金属氢化物、金属有机化合物和它们的混合物中选择的金属催化剂接触。它还涉及一种将甲烷转化为含碳产品的方法，包括将甲烷与包括至少一种金属Me的金属催化剂接触，所述金属Me选择自稀土元素、锕系元素和元素周期表第2至12族金属，以便产生乙烷，其比例至少为65%，特别是相对于在过程中形成的含碳产品而言，重量至少为98%或99%。该过程可以是单步过程，最好在涉及非氧化性催化偶联甲烷的条件下进行，特别是在乙烷生产过程中保持基本恒定的操作条件下进行，最好是连续进行，例如在温度范围从-30°C到+80°C，最好从20°C到500°C，在总绝对压力范围从10-3到100 MPa，最好从0.1到50 MPa。金属催化剂可以选择自金属催化剂，其支撑在固体支撑物上，并最好嫁接到固体支撑物上。本发明的一个主要优点是以非常高的选择性生产乙烷。
• Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC-OH Ligand
  作者：Ravi Srivastava、Raphaël Moneuse、Julien Petit、Paul-Alexis Pavard、Vincent Dardun、Madleen Rivat、Pauline Schiltz、Marius Solari、Erwann Jeanneau、Laurent Veyre、Chloé Thieuleux、Elsje Alessandra Quadrelli、Clément Camp

  DOI：10.1002/chem.201705507

  日期：2018.3.20

  protonolysis chemistry between the ligand's hydroxy group and imido‐alkyl or alkylidene‐alkyl tantalum precursor complexes yielded the rare monometallic tantalum–NHC complexes [Ta(XtBu)(L)(CH2tBu)2] (X=N, CH), in which the alkoxy‐carbene ligand acts as a chelate. In contrast, HL only binds to rhodium through the NHC unit in [Rh(HL)(cod)Cl] (cod=cycloocta‐1,5‐diene), the hydroxy pendant arm remaining unbound. This

  提出了一种新的不对称羟基束缚的N-杂环卡宾（NHC）配体HL的直接合成方法。游离配体表现出不同寻常的OH-卡宾氢键相互作用。该OH-卡宾基序用于产生1）第一个同时显示Fischer和Schrock型卡宾配体的钽配合物，以及2）基于NHC的独特的早期/晚期异双金属配合物。更具体地说，配体的羟基与亚氨基-烷基或亚烷基-烷基钽前体复合物之间的质子分解化学产生了稀有的单金属钽-NHC复合物[Ta（X t Bu）（L）（CH 2 t Bu）2]（X = N，CH），其中烷氧基卡宾配体充当螯合物。相反，HL仅通过[Rh（HL）（cod）Cl]（cod = cycloocta-1,5-diene）中的NHC单元与铑结合，羟基悬垂臂未结合。这种双功能配体支架成功地促进了铑/钽异双金属配合物的组装，其中之一是：1）将[Rh（cod）Cl] 2插入[Ta（N t Bu）（L）（CH 2 t）的Ta-NHC键中。Bu）2
• Metal–Metal Synergy in Well-Defined Surface Tantalum–Iridium Heterobimetallic Catalysts for H/D Exchange Reactions
  作者：Sébastien Lassalle、Ribal Jabbour、Pauline Schiltz、Pierrick Berruyer、Tanya K. Todorova、Laurent Veyre、David Gajan、Anne Lesage、Chloé Thieuleux、Clément Camp

  DOI：10.1021/jacs.9b08311

  日期：2019.12.11

  A novel heterobimetallic tantalum/iridium hydrido complex, [Ta(CH2tBu)3}IrH2(Cp*)}] 1, featuring a very short metal-metal bond, has been isolated through an original alkane elimination route from Ta(CHtBu)(CH2tBu)3 and Cp*IrH4. This molecular precursor has been used to synthesize well-defined silica-supported low-coordinate heterobimetallic hydrido species [≡SiOTa(CH2tBu)2IrH2(Cp*)}] 5 and [≡Si

  一种新型的杂双金属钽/铱氢化物配合物 [Ta(CH2tBu)3}IrH2(Cp*)}] 1 具有非常短的金属-金属键，已通过原始的烷烃消除路线从 Ta(CHtBu) 中分离出来(CH2tBu)3 和 Cp*IrH4。这种分子前体已被用于合成明确定义的二氧化硅负载的低配位异双金属氢化物 [≡SiOTa(CH2tBu)2IrH2(Cp*)}] 5 和 [≡SiOTa(CH2tBu)HIrH2(Cp*) }] 6 使用表面有机金属化学方法 (SOMC)。SOMC 方法可防止在溶液中遇到不想要的二聚化并导致四核物质 [Ta(CH2tBu)2}(Cp*IrH)]2, 4。因此，这种方法允许获得在溶液中无法获得的独特低配位物质。由于结合了金属-金属和金属-载体的协同作用，这些原始负载的 Ta/Ir 物质在 H/D 交换反应中表现出显着增强的催化性能（i）单金属类似物以及（ii）均相系统。特别是，材料