dibenzylmagnesiumbis(tetrahydrofuran) | 110825-75-7

• 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: dibenzylmagnesiumbis(tetrahydrofuran)
• 英文别名: Mg(CH₂Ph)₂(THF)₂；[Mg(benzyl)₂(thf)₂]；Bn₂Mg(THF)₂；Mg(Bn)₂(THF)2
• CAS: 110825-75-7
• 化学式: C₂₂H₃₀MgO₂
• 分子量: 350.784
• InChiKey: ADLWWSPMONBTNU-UHFFFAOYSA-N

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：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  dibenzylmagnesiumbis(tetrahydrofuran) 、 [2-[bis[(2-trimethylsilylazanidylphenyl)methyl]phosphanylmethyl]phenyl]-trimethylsilylazanide;titanium(4+);chloride 以 甲苯 为溶剂， 反应 10.0h， 以66%的产率得到
  参考文献：
  名称：

  A Tripodal Benzylene-Linked Trisamidophosphine Ligand Scaffold: Synthesis and Coordination Chemistry with Group(IV) Metals

  摘要：

  A new tripodal trisamidophosphine ligand (1) based on the trisbenzylphosphine backbone has been synthesized in three steps starting from NaPH2, and phthaloyl-protected 2-aminobenzyl bromide. At elevated temperatures, 1 reacts directly with M(NMe2)(4) (M = Zr, Hf) to afford the dimethylamido complexes [PN3]M(NMe2) (M = Zr, Hf) (2), which are easily converted into the corresponding triflates [PN3]MOTf (M = Zr, Hf) (3) via reaction with triethylsilyl trifluoromethanesulfonate. The related titanium chloro complex [PN3]TiCl (4-Ti) is obtained from 1 and Bn3TiCl via protonolysis. Triple deprotonation of 1 with n-butyllithium affords the tris-lithium salt Li-3[PN3] (1-Li), which serves as a common starting material for the preparation of all the group(IV) chlorides [PN3]MCl (M = Ti, Zr, Hf) (4). Upon treatment of 4-Ti with Bn2Mg(thf)(2), formation of a benzyltitanium species is observed, which is converted cleanly into a ligand-CH-activated species (5-Ti).

  DOI：

  10.1021/ic500163c
• 作为产物：
  描述：

  四氢呋喃 、 苄基氯化镁 以 乙醚 、 正戊烷 为溶剂， 反应 5.0h， 以35%的产率得到dibenzylmagnesiumbis(tetrahydrofuran)
  参考文献：
  名称：

  烷基迁移在有机二甲基2,6-双（亚氨基）吡啶配合物中的迁移机理：带有正方形平面Mg（II）中心的格利雅型配合物的形成

  摘要：

  Dialkylmagnesium compounds [MgR2L2] (R = n-Bu, L = none or R = Bn, L = THF) react with 2,6-bis(imino)pyridines (BIP) to afford different types of Mg(II) alkyl complexes, depending on the nature of R. For R = n-Bu, thermally stable products resulting from selective alkyl transfer to the pyridine nitrogen (N1) atom are obtained. However, NMR studies showed that the reaction of [Mg(Bn)(2)THF2] with (BIP)-B-iPr at -65 degrees C leads to a thermally unstable product arising from benzyl migration to position C2 in the pyridine ring. Above +5 degrees C, this compound rearranges, cleanly yielding a mixture of two isomeric complexes, in which the benzyl group has migrated to positions C3 or C4 of the central ring, respectively. Similar isomeric mixtures were obtained when [Mg(Bn)(2)THF2] was reacted with (BIP)-B-iPr or (BIP)-B-Mes at room temperature. Such mixtures are thermally stable below 80 degrees C, but at this temperature, the 3-benzyl isomer converts into the thermodynamically favored 4-benzyl product, albeit not quantitatively. An alternate route was devised for the selective syntheses of the latter type of compounds. The X-ray diffraction structure of one of them provided an unusual example of a square-planar alkylmagnesium(II) center.

  DOI：

  10.1021/acs.organomet.6b00528
• 作为试剂：
  描述：

  氯代叔丁烷 在 dibenzylmagnesiumbis(tetrahydrofuran) 、 [Ce(C₅Me₄H)₃] 作用下， 以 四氢呋喃 为溶剂， 以20 %的产率得到异丁烯
  参考文献：
  名称：

  Photocatalytic dechlorination of unactivated chlorocarbons including PVC using organolanthanide complexes

  摘要：

  简单的镧系元素环戊二烯（Cp）配合物可以光化学方法裂解未活化的氯化碳氢化合物（包括聚氯乙烯（PVC））的 sp3 碳-氯键。

  DOI：

  10.1039/d3cc02906a

文献信息

• Synthesis and characterization of titanium(IV) complexes containing the diphenylphosphino- and diphenylthiophosphoryl-functionalized cyclopentadienyl ligand. Crystal and molecular structure of Ti(η5-C5H4PPh2)Cl3
  作者：Juan C Flores、Rocı́o Hernández、Pascual Royo、Angelika Butt、Thomas P Spaniol、Jun Okuda

  DOI：10.1016/s0022-328x(99)00414-3

  日期：2000.1

  moisture-sensitive mono(cyclopentadienyl) compound Ti(η5-C5H4PPh2)Cl3 (4). Reaction of 4 with Mg(CH2C6H5)2(THF)2 gave Ti(η5-C5H4PPh2)(CH2C6H5)3 (5). Reactions of the lithium and thallium derivatives MC5H4P(S)Ph2} (M=Li (2), Tl (3)) with one equiv. of TiCl4 afforded the mono(cyclopentadienyl) complex Tiη5-C5H4P(S)Ph2}Cl3 (6), whereas reaction with 0.5 equiv. of TiCl4 gave the bis(cyclopentadienyl) complex Tiη5-C5H4P(S)Ph2}2Cl2

  三甲基甲硅烷环戊二烯衍生物Ç 5 ħ 4（森达3）PPH 2（1）中的溶液用TiCl 4处理4，得到空气和水分敏感的单（环戊二烯基）钛化合物（η 5 -C 5 H ^ 4 PPH 2）氯3（4）。的反应4的Mg（CH 2 ç 6 ħ 5）2（THF）2，得到的Ti（η 5 -C 5 H ^ 4 PPH 2）（CH 2 ç6 H 5）3（5）。锂和th衍生物M C 5 H 4 P（S）Ph 2 }（M = Li（2），Tl（3））与一个当量的反应。的TiCl 4，得到单（环戊二烯基）钛络合物η 5 -C 5 H ^ 4 P（S）PH 2 }氯3（6），而用0.5当量反应。的TiCl 4，得到双（环戊二烯基）钛络合物η 5 -C 5 H ^ 4 P（S）PH 2 } 2Cl 2（8）。化合物6也被分离为选自Ti η的反应次要产物5 -C 5 H ^ 4 P（S）PH 2 } 2氯2（8）与一个当量。TiCl
• Organomagnesium-Catalyzed Isomerization of Terminal Alkynes to Allenes and Internal Alkynes
  作者：Raphaël Rochat、Koji Yamamoto、Michael J. Lopez、Haruki Nagae、Hayato Tsurugi、Kazushi Mashima

  DOI：10.1002/chem.201500179

  日期：2015.5.26

  the transformation of these terminal alkynes into allenes and further to internal alkynes under mild conditions. To the best of our knowledge, this example is the first of an organomagnesium‐catalyzed isomerization of alkynes. Notably, the reactions proceeded through temporally separated autotandem catalysis, thus allowing the isolation of the allene or internal alkyne species in good yields. Mechanistic

  通过N，N-二烷基胺亚胺配体1和二苄基镁的亚胺部分的苄基化反应合成有机镁络合物2。3-芳基-1-丙炔与2反应形成相应的四炔基络合物，在温和条件下，这些络合物可作为催化剂将这些末端炔烃转化为丙二烯，并进一步转化为内部炔烃。据我们所知，该实例是炔烃有机镁催化异构化的第一个实例。值得注意的是，反应通过暂时分离的自动串联催化进行，从而允许以高收率分离出烯丙基或内部炔烃。机理实验表明，具有催化活性的四炔基络合物由炔基镁，烯丙基镁和炔丙基镁物种的互变异构混合物组成。
• Benzylene-linked [PNP] scaffolds and their cyclometalated zirconium and hafnium complexes
  作者：Malte Sietzen、Sonja Batke、Patrick W. Antoni、Hubert Wadepohl、Joachim Ballmann

  DOI：10.1039/c7dt00413c

  日期：——

  synthesis of zirconium and hafnium complexes. For both ligands, the dimethylamides [A]M(NMe2)3 ([A]1-M) and [B]M(NMe2)3 ([B]1-M) were prepared and converted to the iodides [A]MI3 ([A]2-M) and [B]MI3 ([B]2-M) (M = Zr, Hf). Starting from these iodides, the corresponding benzyl derivatives [A]MBn3 ([A]3-M) and [B]MBn3 ([B]3-M) (M = Zr, Hf) were obtained via reaction with Bn2Mg(OEt2)2. For zirconium, the benzylic

  的亚苄基联[PNP]支架HN（CH 2 - ö -C 6 ħ 4 PPH 2）2（[甲] H）和HN（C 6 H ^ 4 - ö -CH 2 PPH 2）2（[乙1 H ）已用于合成锆和ha络合物。对于两个配体，二甲酰胺[ A ] M（NMe 2）3（[A] 1-M）和[ B ] M（NMe 2）3（[B] 1-M制备）并将其转化为碘化物[ A ] MI 3（[A] 2-M）和[ B ] MI 3（[B] 2-M）（M = Zr，Hf）。从这些碘化物开始，通过与Bn 2反应获得相应的苄基衍生物[ A ] MBn 3（[A] 3-M）和[ B ] MBn 3（[B] 3-M）（M = Zr，Hf）Mg（OEt 2）2。对于锆，[A] 3-Zr和[B]中的苄基配体位置3 -锆被发现容易cyclometalate，这导致了相应的κ 4 - [PCNP] ZrBn 2种配合物[A] 4 -锆和[B]
• Trapping Unstable Terminal M−O Multiple Bonds of Monocyclopentadienyl Niobium and Tantalum Complexes with Lewis Acids
  作者：Javier Sánchez-Nieves、Luis M. Frutos、Pascual Royo、Obis Castaño、Eberhardt Herdtweck、Marta E. G. Mosquera

  DOI：10.1021/ic1016609

  日期：2010.11.15

  CpR = Cp′, X = Cl 2a) afforded the oxo-alane complexes [MCpRX2O·Al(C6F5)3}] (M = Ta, CpR = Cp*, X = Cl 3a, Bz 3b, Me 3c; M = Nb, CpR = Cp′, X = Cl 4a), releasing B(C6F5)3. Compound 3a was also obtained by addition of Al(C6F5)3 to the dinuclear μ-oxo compound [TaCp*Cl2(μ-O)]2, meanwhile addition of the water adduct H2O·Al(C6F5)3 to [TaCp*Me4] gave complex 3c. The structure of 2a and 3a was obtained

  的水解[NbCP'Cl 4 ]（CP'=η 5 -C 5 H ^ 4森达3）与水的加合物ħ 2 O·B（C 6 ˚F 5）3，得到氧代硼烷化合物〔NbCP'Cl 2 O·B（C 6 F 5）3 }]（2a）。该化合物与[MgBz 2（THF）2 ]反应，得到[NbCP'Bz 2 O·B（C 6 F 5）3 }]（2b），而[NbCP'Me 2 O·B（C 6 F由[NbCP'Me 4 ]与H 2 O·B（C 6 F 5）3的反应获得（5）3 }]（2c）。的Al（C的另外6 ˚F 5）3，以含有氧代硼烷化合物[MCP解决方案- [R X 2 O·B（C 6 ˚F 5）3 }]（M =钽中，CP [R =η 5 -C 5我5（CP *），X = Cl 1a，Bz 1b，Me 1c； M = Nb，CP R＝ CP′，X ＝ Cl 2a）得到氧代-烷烃配合物[MCa href=https://www.molaid.com/MS_6449 target="_blank">CP R X 2 O·Al（C
• Square Planar Cobalt(II) Hydride versus T-Shaped Cobalt(I): Structural Characterization and Dihydrogen Activation with PNP–Cobalt Pincer Complexes
  作者：Lukas S. Merz、Clemens K. Blasius、Hubert Wadepohl、Lutz H. Gade

  DOI：10.1021/acs.inorgchem.9b00384

  日期：2019.5.6

  toward alkenes, whereas the cobalt(II) hydride 3iPr-CoIIH was successfully employed in the catalytic hydrogenation of unhindered alkenes. The stoichiometric hydrogenolysis of 8iPr-CoIIBn at elevated pressure (10 bar) led to a rapid cleavage of the Co–C bond to yield hydride complex 3iPr-CoIIH. On the other hand, treatment of 2iPr-CoIICl with phenethylmagnesium chloride directly resulted in the formation

  基于咔唑的钳位配体R（Cbz PNP）H（R = i Pr，t Bu）已用于合成和表征各种低自旋和高自旋钴配合物。用NaHBEt 3处理高自旋络合物R（Cbz PNP）CoCl（2 R -Co II Cl）后，选择性形成氢化钴（II）3 i Pr -Co II H和T形钴（I）复合4 t Bu -Co I观察到取决于磷原子上的取代基。为了明确表征反应产物，进行了密度泛函理论（DFT）支持的顺磁NMR分析，该分析建立了金属原子的电子构型和氧化态，从而证明了配体取代对产物的重大影响。反应。一个明显的单电子反应性被发现的4吨卜-Co我在脱卤吨BuCl和切割PhSSPh的。另一方面，Co I物种在二氢的氧化加成中表现出两电子氧化还原行为。生成的二氢化物络合物6 t Bu发现-Co III（H）2对烯烃显示迟钝的反应性，而氢化钴（II）3 i Pr -Co II H成功地用于未受阻烯烃的催化加氢。的化学计量的氢解8我镨-Co