[(1,2-bis(di-tert-butylphosphino)ethane)Ni(CH2CH2COO)] | 1428307-69-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: [(1,2-bis(di-tert-butylphosphino)ethane)Ni(CH2CH2COO)]
• 英文别名: 1-bis(di-tert-butylphosphino)ethan-1-ethylenenickela-2-oxacyclopentan-3-one；[(1,2-bis(di-tert-butylphosphino)ethane)Ni(CH₂CH₂COO)]；[(dtbpe)Ni(CH₂CH₂COO)]
• CAS: 1428307-69-0
• 化学式: C₂₁H₄₄NiO₂P₂
• 分子量: 449.217
• InChiKey: PXIWVDBCRRLIMW-UHFFFAOYSA-M

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：

  [(1,2-bis(di-tert-butylphosphino)ethane)Ni(CH2CH2COO)] 在 sodium 2-fluorophenolate 作用下， 以 氘代四氢呋喃 为溶剂， 反应 20.0h， 以100%的产率得到(bis(di-tert-butylphosphino)ethane)(η2-ethene)nickel(0)
  参考文献：
  名称：

  镍催化的烯烃直接与CO2的羧化反应：一锅法合成α，β-不饱和羧酸盐

  摘要：

  在碱的存在下，已经实现了镍的烯烃与便宜且可大量利用的C 1结构单元二氧化碳（CO 2）的镍直接催化羧化反应。一锅法反应可直接和选择性地合成各种α，β-不饱和羧酸盐（TON> 100，TOF高达6 h -1，TON =周转数，TOF =周转频率）。因此，可以在一个步骤中由乙烯，CO 2和钠盐合成丙烯酸钠。丙烯酸酯是工业上重要的产品，迄今为止其合成需要多个步骤。

  DOI：

  10.1002/chem.201405528
• 作为产物：
  描述：

  N,N,N',N'-tetramethylethylenediamine nickelacyclopropionate 、 1,2-双(二-叔丁基磷酰)乙烷 以 四氢呋喃 为溶剂， 反应 1.0h， 以80%的产率得到[(1,2-bis(di-tert-butylphosphino)ethane)Ni(CH2CH2COO)]
  参考文献：
  名称：

  通过甲基化剂通过M–O开环（M = Ni，Pd） 从金属内酯配合物中释放丙烯酸甲酯†

  摘要：

  各种镍基和戊内酯的开环，是由M-O键的裂解引起的 三氟甲磺酸甲酯 （MeOTf）和 甲基碘（MeI）被检查。实验证据支持烷基化剂开环，随后消除β-H从而导致开环的机理。丙烯酸甲酯和金属氢化物。MeOTf的内酯开环效率远远高于包括先前报道的任何其他甲基化剂甲基碘。

  DOI：

  10.1039/c3nj00693j

文献信息

• [EN] PREPARATION OF alpha,beta-ETHYLENICALLY UNSATURATED CARBOXYLIC SALTS BY CATALYTIC CARBOXYLATION OF ALKENES<br/>[FR] PRÉPARATION DE SELS D'ACIDES CARBOXYLIQUES À INSATURATION Alpha,Beta-ÉTHYLÉNIQUE PAR CARBOXYLATION CATALYTIQUE D'ALCÈNES
  申请人：BASF SE

  公开号：WO2013098772A1

  公开（公告）日：2013-07-04

  In a process for preparing an alkalimetalor alkaline earth metal salt of an α,β-ethylenically unsaturated carboxylic acid, a)a transition metal-alkene complex is reacted with CO2 to give a metallalactone, b)the metallalactone is reacted with a base to give an adduct of the alkalimetal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid with the transition metal complex, and c)the adduct is reacted with an alkene to release the alkalimetalor alkaline earth metalsalt of the α,β-ethylenically unsaturated carboxylic acid and regenerate the transition metal-alkene complex. The baseis selected from alkalimetal or alkaline earth metal hydroxides and alkali metal or alkaline earth metal superbases.The alkene is, for example, ethene. The transition metal complex comprises, for example, nickel and a bidentate P,P, P,N, P,O or P,carbene ligand, such as 1,2-bis(di-tert-butylphosphino)ethane.

  在制备α，β-乙烯基不饱和羧酸的碱金属或碱土金属盐的过程中，a）将过渡金属-烯烃配合物与二氧化碳反应以得到金属内酯，b）金属内酯与碱反应以得到碱金属或碱土金属盐的α，β-乙烯基不饱和羧酸与过渡金属配合物的加合物，c）加合物与烯烃反应以释放碱金属或碱土金属盐的α，β-乙烯基不饱和羧酸并再生过渡金属-烯烃配合物。碱选择自碱金属或碱土金属氢氧化物和碱金属或碱土金属超碱。烯烃可以是乙烯。过渡金属配合物包括镍和双齿P，P，P，N，P，O或P，卡宾配体，例如1,2-双（二叔丁基膦基）乙烷。
• Preparation of a,B-Ethylenically Unsaturated Carboxylic Salts By Catalytic Carboxylation Of Alkenes
  申请人：BASF SE

  公开号：US20130172616A1

  公开（公告）日：2013-07-04

  In a process for preparing an alkali metal or alkaline earth metal salt of an α,β-ethylenically unsaturated carboxylic acid, a) a transition metal-alkene complex is reacted with CO 2 to give a metallalactone, b) the metallalactone is reacted with a base to give an adduct of the alkali metal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid with the transition metal complex, and c) the adduct is reacted with an alkene to release the alkali metal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid and regenerate the transition metal-alkene complex. The base is selected from alkali metal or alkaline earth metal hydroxides and alkali metal or alkaline earth metal superbases. The alkene is, for example, ethene. The transition metal complex comprises, for example, nickel and a bidentate P,P, P,N, P,O or P,carbene ligand, such as 1,2-bis(di-tert-butylphosphino)ethane.

  在制备α，β-乙烯基不饱和羧酸的碱金属或碱土金属盐的过程中，a) 过渡金属-烯烃配合物与CO2反应形成金属内酯，b) 金属内酯与碱反应形成α，β-乙烯基不饱和羧酸的碱金属或碱土金属盐与过渡金属配合物的加合物，c) 加合物与烯烃反应释放出α，β-乙烯基不饱和羧酸的碱金属或碱土金属盐，并再生过渡金属-烯烃配合物。碱为选自碱金属或碱土金属的氢氧化物和碱金属或碱土金属的超碱。烯烃可以是乙烯等。过渡金属配合物包括镍和双齿P，P，P，N，P，O或P，卡宾配体，例如1,2-双(二叔丁基膦基)乙烷。
• Mechanistic Details of the Nickel-Mediated Formation of Acrylates from CO₂, Ethylene and Methyl Iodide
  作者：Philipp N. Plessow、Laura Weigel、Ronald Lindner、Ansgar Schäfer、Frank Rominger、Michael Limbach、Peter Hofmann

  DOI：10.1021/om400262b

  日期：2013.6.10

  Methyl iodide induces the stoichiometric cleavage of nickelalactones, which are key intermediates in the nickel-mediated reaction of CO2 and alkenes to acrylates. Herein, we propose a modified and extended mechanism for this reaction on the basis of theoretical and experimental investigations for the bidentate P ligand 1,2-bis(di-tert-butylphosphino)ethane (dtbpe). The calculated elementary steps agree well with experimental findings: reaction barriers are reasonable and explain the facile liberation of acrylate from a nickelalactone by methyl iodide. We were able to isolate reactive intermediates and to verify the existence of proposed reaction pathways. Additionally, we have identified unproductive pathways leading to byproducts (e.g., propionates and catalytically inactive organometallic species). Although those side reactions can be suppressed to a certain extent, the strong binding of acrylate to nickel prevents a catalytic reaction, at least for the chosen ligand.