YBn₃(THF)₃ | 960307-89-5

• 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: YBn₃(THF)₃
• 英文别名: methanidylbenzene;oxolane;yttrium(3+)
• CAS: 960307-89-5
• 化学式: C₃₃H₄₅O₃Y
• 分子量: 578.624
• InChiKey: UNOSQDSHJGOGOB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.99
• 重原子数：
  37
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,4,6-trimethyl-N-(2-pyroolidin-1-ylethyl)-1,4-diazepan-6-amine 、 YBn₃(THF)₃ 以 甲苯 为溶剂， 以80%的产率得到(1,4,6-trimethyl-N-(2-(pyrrolidin-1-yl)ethyl)-1,4-diazepane-6-amine(-H))Y(η1-benzyl)(η2-benzyl)
  参考文献：
  名称：

  Scandium, Yttrium, and Lanthanum Benzyl and Alkynyl Complexes with the N-(2-Pyrrolidin-1-ylethyl)-1,4-diazepan-6-amido Ligand: Synthesis, Characterization, and Z-Selective Catalytic Linear Dimerization of Phenylacetylenes

  摘要：

  1,4,6-Trimethyl-N-(2-pyrrolidin-1-ylethyl)-1,4-diazepan-6-amine (HL) reacts with M(CH2Ph)(3)(THF)(3) to give the dibenzyl complexes (L)M(CH2Ph)(2) (M = SC, 1; M = Y, 2; M = La, 3). Compounds 1, 2, and 3 can be converted to their corresponding cationic monobenzyl species [(L)M(CH2Ph)](+) (M = Sc, Y and La) by reaction with [PhNMe2H][B(C6F5)(4)]. Reaction of (L)Sc(CH2Ph)(2) with 2 equiv of phenylacetylene affords the monomeric dialkynyl complex (L)Sc(C CPh)(2) (4), while reactions of (L)M(CH2Ph)(2) (M = Y and La) give the dimeric dialkynyl complexes [(L)M(C CPh)(mu-C CPh)](2) (M = Y, 5; M = La, 6). The neutral complexes (2, 3, 5, and 6) and the cationic monobenzyl species [(L)M(CH2Ph)](+) (M = Y and La) are catalysts for the Z-selective linear head-to-head dimerization of phenylacetylenes. The cationic yttrium and the neutral lanthanum systems are the most effective catalysts in the series. The related scandium species show poor activity and selectivity.

  DOI：

  10.1021/om8004228
• 作为产物：
  描述：

  [YCl3(THF)3.5] 、 benzyl potassium 以 四氢呋喃 为溶剂， 反应 0.5h， 以79.2%的产率得到YBn₃(THF)₃
  参考文献：
  名称：

  顺磁性镧系元素苄基配合物的合成与表征

  摘要：

  与顺磁性镧系元素（Sc，Y，La和Lu）相比，顺磁性镧系元素（Ln，从Ce到Yb）的有机金属化学远没有那么发达。缺乏可用的起始原料和表征方法是主要障碍。本文中我们报道了钕，g 、,和的三苄基配合物的合成和表征。此外，我们介绍了一种直接程序，用于从相应的氧化物开始合成由二茂铁二酰胺配体支撑的镧系元素苄基和碘化物配合物。所有新合成的化合物均通过X射线晶体学，1 H NMR光谱（（化合物为NMR静音）和元素分析进行了表征。

  DOI：

  10.1021/om3010433

文献信息

• Reactions of Aromatic N-Heterocycles with Yttrium and Lutetium Benzyl Complexes Supported by a Pyridine-Diamide Ligand
  作者：Suyun Jie、Paula L. Diaconescu

  DOI：10.1021/om901052e

  日期：2010.3.8

  comparison between the reactivity behavior of yttrium and lutetium benzyl complexes supported by a pyridine diamide, on one hand, and by a ferrocene diamide, on the other hand, toward aromatic N-heterocycles, such as 1-methylimidazole, isoquinoline, acridine, and 2-picoline, is presented. The ring opening of 1-methylimidazole by the pyridine-diamide complexes was observed, analogously to the ring opening of

  一方面，吡啶二酰胺和二茂铁二酰胺负载的钇和benzyl苄基配合物对芳香族N-杂环（例如1-甲基咪唑，异喹啉，a啶和介绍了2-甲基吡啶。观察到吡啶-二酰胺配合物引起的1-甲基咪唑的开环，类似于由二茂铁-二酰胺配体支撑的3族苄基配合物在同一底物上的开环。同样，在与2-甲基吡啶和异喹啉的反应中观察到类似产物。然而，当使用a啶时，两个金属中心获得了不同的产物：钇的烷基转移和的正金属化。
• Benzyl Complexes of Lanthanide(II) and Lanthanide(III) Metals: Trends and Comparisons
  作者：Sjoerd Harder、Christian Ruspic、Nollaig Ní Bhriain、Frederic Berkermann、Markus Schürmann

  DOI：10.1515/znb-2008-0307

  日期：2008.3.1

  A variety of benzyllanthanide complexes have been prepared by the metathesis reaction of benzylpotassium precursors with lanthanide halides. Syntheses and crystal structures for the following complexes are described: [2-Me₂N-α-Me₃Si-benzyl]₂Eu(II)·(THF)₂ (1-Eu), (2-Me₂Nbenzyl) ₃Ln(III) (2-Ln with Ln = Nd, Sm, Dy, Ho, Yb), (4-R-C₆H₄CH₂)₃Ln·(THF)₃ (3-Y: Ln = Y, R = H; 3-La: Ln = La, R = tBu). Complexes of types 1 and 2 are thermally robust on account of a stabilization by a benzylic Me₃Si substituent and/or intramolecular coordination of the Me₂N substituent. Comparison of the crystal structures of these new series of lanthanide complexes shows several similarities and trends. In addition, comparisons with alkali metal and alkaline earth metal benzyl complexes are made.

  通过苯甲基钾前体与镧系卤化物的交换反应制备了多种苯甲基镧系配合物。描述了以下配合物的合成和晶体结构：[2-Me2N-α-Me3Si-苯甲基]2Eu(II)·(THF)2（1-Eu），(2-Me2N苯甲基)3Ln(III)（2-Ln，其中Ln = Nd，Sm，Dy，Ho，Yb），(4-R-C6H4CH2)3Ln·(THF)3（3-Y：Ln = Y，R = H；3-La：Ln = La，R = tBu）。由于苯甲基的Me3Si取代基和/或Me2N取代基的分子内配位，类型1和2的配合物具有热稳定性。比较这些新系列镧系配合物的晶体结构显示出几个相似性和趋势。此外，还与碱金属和碱土金属苯甲基配合物进行了比较。
• A monometallic lanthanide bis(methanediide) single molecule magnet with a large energy barrier and complex spin relaxation behaviour
  作者：Matthew Gregson、Nicholas F. Chilton、Ana-Maria Ariciu、Floriana Tuna、Iain F. Crowe、William Lewis、Alexander J. Blake、David Collison、Eric J. L. McInnes、Richard E. P. Winpenny、Stephen T. Liddle

  DOI：10.1039/c5sc03111g

  日期：——

  We report a dysprosium(III) bis(methanediide) single molecule magnet (SMM) where stabilisation of the highly magnetic states and suppression of mixing of opposite magnetic projections is imposed by a linear arrangement of negatively-charged donor atoms supported by weak neutral donors. Treatment of [Ln(BIPMTMS)(BIPMTMSH)] [Ln = Dy, 1Dy; Y, 1Y; BIPMTMS = C(PPh2NSiMe3)2}2−; BIPMTMSH = HC(PPh2NSiMe3)2}−]

  我们报道了一种镝( III )双(甲烷二化物)单分子磁体(SMM)，其中由弱中性供体支持的带负电的供体原子的线性排列实现了高磁性状态的稳定和相反磁性投影混合的抑制。 [Ln(BIPM TMS )(BIPM TMS H)] 的治疗 [Ln = Dy, 1Dy ; Y， 1Y ； BIPM TMS = C(PPh 2 NSiMe 3 ) 2 } 2− ; BIPM TMS H = HC(PPh 2 NSiMe 3 ) 2 } − ] 与苄基钾/18-冠-6 醚 (18C6) 在 THF 中得到 [Ln(BIPM TMS ) 2 ][K(18C6)(THF) 2 ] [Ln=Dy， 2Dy ； Y， 2Y ]。零直流场中2Dy的交流磁测量显示出与温度和频率相关的 SMM 行为。奥尔巴赫弛豫在高温下占主导地位，但在较低温度下，二阶拉曼过程占主导地位。配合物2Dy具有两个热激活能垒 ( U eff
• Synthesis and reactivity of the yttrium-alkyl-carbene complex [Y(BIPM)(CH2C6H5)(THF)] (BIPM = {C(PPh2NSiMe3)2})
  作者：David P. Mills、Oliver J. Cooper、Jonathan McMaster、William Lewis、Stephen T. Liddle

  DOI：10.1039/b902079a

  日期：——

  Reaction of [YI3(THF)3.5] with three equivalents of [KBz] (Bz = CH2C6H5) affords the tri-benzyl complex [Y(Bz)3(THF)3] (2) in excellent yield. Complex 2 reacts with H2C(PPh2NSiMe3)2 (H2BIPM) to afford the yttrium-alkyl-carbene complex [Y(BIPM)(Bz)(THF)] (3, BIPM = C(PPh2NSiMe3)2}). Compound 3 reacts with one equivalent of benzophenone to give the alkoxy 1,2-migratory insertion product [Y(BIPM)(OCPh2Bz)(THF)] (4) rather than the alkene Wittig-product Ph2CC(PPh2NSiMe3)2. Reaction of 4 with one or more equivalents of benzophenone does not afford any detectable alkene products, rather it apparently catalyses rearrangement of monomeric 4 to afford dimeric [Y(μ-BIPM)(OCPh2Bz)}2] (5). Investigations reveal that formation of 5 is proportional to the amount of benzophenone added, but the benzophenone is recovered at the end of the reaction. Reaction of 3 with diphenyldiazene affords the 1,2-migratory insertion product [Y(BIPM)N(Ph)N(Ph)(Bz)}(THF)] (6) Compounds 2, 3, 4, 5, and 6 have been variously characterised by X-ray crystallography, multi-nuclear NMR spectroscopy, FTIR spectroscopy, and CHN micro-analyses. Density functional theory calculations on 3 reveal the HOMO to be localised at the Y–Calkyl bond which is commensurate with the observed reactivity.

  [YI3(THF)3.5]与三当量的[KBz]（Bz = CH2C6H5）反应生成三苄基络合物[Y(Bz)3(THF)3]（2），收率极高。络合物 2 与 H2C(PPh2NSiMe3)2 (H2BIPM) 反应生成钇-烷基-烯络合物 [Y(BIPM)(Bz)(THF)]（3，BIPM = C(PPh2NSiMe3)2}）。化合物 3 与一当量的二苯甲酮反应，生成烷氧基 1,2-Migratory 插入产物 [Y(BIPM)(OCPh2Bz)(THF)]（4），而不是烯 Wittig 产物 Ph2CC(PPh2NSiMe3)2。4 与一当量或多当量的二苯甲酮反应不会产生任何可检测到的烯烃产物，相反，它显然催化了单体 4 的重排，从而产生二聚体 [Y(μ-BIPM)(OCPh2Bz)}2] (5)。研究表明，5 的形成与加入的二苯甲酮的量成正比，但二苯甲酮在反应结束时被回收。化合物 2、3、4、5 和 6 已通过 X 射线晶体学、多核 NMR 光谱、傅立叶变换红外光谱和 CHN 显微分析进行了各种表征。对 3 的密度泛函理论计算显示，HOMO 定位于 Y-烷基键，这与观察到的反应活性相符。
• Improving Alkyl–Alkyl Cross-Coupling Catalysis with Early Transition Metals through Mechanistic Understanding and Metal Tuning
  作者：Roman G. Belli、Victoria C. Tafuri、Courtney C. Roberts

  DOI：10.1021/acscatal.2c02785

  日期：2022.8.5

  cross-coupling is a powerful C–C bond-forming transformation typically catalyzed by late transition metals. Herein, we report a mechanistic investigation into an early transition metal-catalyzed variant of this reaction. Through this mechanistic understanding, an ideal Y catalyst was determined through tuning of the metal in order to optimize the oxidation potential, which governs the rate-limiting step

  烷基-烷基交叉偶联是一种强大的 C-C 键形成转化，通常由后过渡金属催化。在此，我们报告了对该反应的早期过渡金属催化变体的机理研究。通过这种机理理解，通过调整金属来确定理想的 Y 催化剂，以优化氧化电位，这决定了该反应中的限速步骤。揭示了广泛的底物范围，包括各种官能团以及活性较低的底物。