(bis(di-tert-butylphosphino)ethane)(η2-ethene)nickel(0) | 138419-50-8

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: (bis(di-tert-butylphosphino)ethane)(η2-ethene)nickel(0)
• 英文别名: (dtbpe)Ni(ethylene) complex；Ni(dtbpe)(ethylene)；[Ni(CH2CH2)(1,2-bis(di-tert-butylphosphino)ethane)]；[Ni(η2-C2H4)(t-Bu2PCH2CH2P-t-Bu2)]；[(ethylene)Ni(drbpe)]；[EtNi(drbpe)]；ditert-butyl(2-ditert-butylphosphanylethyl)phosphane;ethene;nickel
• CAS: 138419-50-8
• 化学式: C₂₀H₄₄NiP₂
• 分子量: 405.207
• InChiKey: UVMWRGCZEZNZKY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.94
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 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：

  (bis(di-tert-butylphosphino)ethane)(η2-ethene)nickel(0) 以 neat (no solvent) 、 not given 为溶剂， 生成
  参考文献：
  名称：

  Synthesis, Structure, and Reactivity of (^tBu₂PC₂H₄P^tBu₂)Ni(CH₃)₂ and {(^tBu₂PC₂H₄P^tBu₂)Ni}₂(μ-H)₂

  摘要：

  Oxidative addition of CH3I to (d(t)bpe)Ni(C2H4) (d(t)bpe = (Bu2PC2H4PBu2)-Bu-t-Bu-t) affords (d(t)bpe)-Ni(I)CH3 (I). The reaction of (d(t)bpe)NiCl2 or 1 with the stoichiometric quantity of (tmeda)Mg(CH3), yields (d(t)bpe)Ni(CH3)(2) (2). (d(t)bpe)Ni(I)CD3 (1-d(3)) and (d(t)bpe)Ni(CD3)(2) (2-d(6)) have been prepared analogously. Thermolysis of 2 in benzene affords {(d(t)bpe)Ni}(2)(mu-eta(2):eta(2)-C6H6) (4). The reaction of either 2 or 4 with hydrogen (H-2, HD, D-2) gives {(d(t)bpe)Ni}(2)(mu-H)(2) (3) and the isotopomers {(d(t)bpe)Ni}(2)(mu-H)(mu-D) (3-d) and {(d(t)bpe)Ni}(2)(mu-D)(2) (3-d(2)). According to the NMR spectra, the structure of 3 is dynamic in solution. The crystal structures of 2 and 3 have been determined by X-ray crystallography, Solution thermolysis of 2 or reduction of (dtbpe)NiCl2 with Mg* in the presence of alkanes probably involves a-complex-type intermediates [(d(t)bpe)Ni(eta(2)-R'H)] (R' = e.g. C2H5, A). While the nonisolated [(d(t)bpe)Ni-0] a-complexes A are exceedingly reactive intermediates, isolated 3 and 4 represent easy to handle starting complexes for [(d(t)bpe)Ni-0] reactions. Partial protolysis of 2 with CF3SO3H affords (d(t)bpe)Ni(CH3)(OSO2CF3) (5). Complex 5 reacts slowly with 2 equiv of ethene to give equimolar amounts of [(d(t)bpe)Ni(C2H5)](+)(OSO2CF3-) (6) and propene. The reaction is thought to be initiated by an insertion of ethene into the Ni-CH3 bond of 5 to form the intermediate [(d(t)bpe)Ni(C3H7)(OSO2CF3)] (G), followed by elimination of propene to give the hydride intermediate [(d(t)bpe)Ni(H)(OSO2CF3)] (H), which on insertion of ethene into the Ni-H bond affords 6.

  DOI：

  10.1021/om980705y
• 作为产物：
  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

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。
• The First Catalytic Synthesis of an Acrylate from CO₂and an Alkene-A Rational Approach
  作者：Michael L. Lejkowski、Ronald Lindner、Takeharu Kageyama、Gabriella É. Bódizs、Philipp N. Plessow、Imke B. Müller、Ansgar Schäfer、Frank Rominger、Peter Hofmann、Cornelia Futter、Stephan A. Schunk、Michael Limbach

  DOI：10.1002/chem.201201757

  日期：2012.10.29

  than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C1 building block carbon dioxide and alkenes has been an unsolved problem in catalysis research, both in academia and industry. Herein, we describe a homogeneous catalyst based on nickel that permits the catalytic synthesis of the industrially highly relevant acrylate sodium acrylate from CO2, ethylene, and

  在过去的三十多年中，无论是在学术界还是工业界，由廉价且大量可得的C 1结构单元二氧化碳和烯烃催化合成丙烯酸酯一直是催化研究中尚未解决的问题。本文中，我们描述了一种基于镍的均相催化剂，该催化剂允许从CO 2，乙烯和碱催化合成工业上高度相关的丙烯酸钠丙烯酸酯钠，如该阶段所示，相对于10倍的周转率到金属。
• Group Transfer from Nickel Imido, Phosphinidene, and Carbene Complexes to Ethylene with Formation of Aziridine, Phosphirane, and Cyclopropane Products
  作者：Rory Waterman、Gregory L. Hillhouse

  DOI：10.1021/ja0381914

  日期：2003.11.1

  carbene ligands with ethylene are reported. In all three cases, corresponding three-membered rings, aziridine, phosphirane, and cyclopropane, were produced in moderate to excellent yields. NMR spectra of the phosphinidene (dtbpe)Ni=P(dmp) reaction with ethylene show a [2+2] cycloaddition adduct before phosphirane formation. A labeling study with trans-ethylene-d2 shows formation of aziridine and phosphirane

  报道了带有末端亚氨基、膦亚基和卡宾配体的镍配合物与乙烯的反应。在所有三种情况下，相应的三元环、氮丙啶、膦和环丙烷均以中等至极好的收率生产。膦亚基 (dtbpe)Ni=P(dmp) 与乙烯反应的 NMR 谱显示在形成膦之前 [2+2] 环加成加合物。用反式乙烯-d2 进行的标记研究表明，氮丙啶和膦的形成伴随着相对立体化学的净保留。
• Synthesis of coordinatively unsaturated diphosphine nickel(<scp>II</scp>) and palladium(<scp>II</scp>)β-agostic ethyl cations: X-ray crystal structure of [Ni{Bu^t₂P(CH₂)₂PBu^t₂}(C₂H₅)][BF₄]
  作者：Fiona M. Conroy-Lewis、Laura Mole、Alan D. Redhouse、Stephen A. Litster、John L. Spencer

  DOI：10.1039/c39910001601

  日期：——

  Protonation of [M(L2)(η2-C2H4)](L2= chelating diphosphine; M = Ni, Pd) with HBF4 affords a series of cations [M(L2)(C2H5)]+ characterized as β-agostic ethyl complexes by NMR spectroscopy and X-ray structure analysis.

  的质子化[M（L 2）（η 2 -C 2 H ^ 4）]（L 2 =螯合二膦; M =镍，钯）与HBF 4次，得到了一系列的阳离子[M（L的2）（C 2 H ^ 5）] +通过NMR光谱和X射线结构分析表征为β-声级乙基络合物。
• The Nature of β‐Agostic Bonding in Late‐Transition‐Metal Alkyl Complexes
  作者：Wolfgang Scherer、Verena Herz、Andreas Brück、Christoph Hauf、Florian Reiner、Sandra Altmannshofer、Dirk Leusser、Dietmar Stalke

  DOI：10.1002/anie.201006065

  日期：2011.3.14

  Experimental charge density analyses reveal significant differences between the nature of β‐agostic bonding in early‐ and late‐transition‐metal (M) complexes. For dn‐configurated M alkyl compounds, the β‐agostic interaction can be described by a modified Dewar–Chatt–Duncanson model with three σ/π bonding components, whereas one delocalized orbital is sufficient to account for the hyperconjugative stabilization

  实验电荷密度分析揭示了早期和晚期过渡金属（M）络合物中β声波键合的性质之间存在显着差异。对于d n构型的M烷基化合物，β-声波相互作用可以通过具有三个σ/π键组分的改良的Dewar-Chatt-Duncanson模型来描述，而一个离域轨道足以说明过早d 0时的超共轭稳定。系统。