[Sm(N,N′-bis(2,6-diisopropylphenyl)formamidinate)2(tetrahydrofuran)2] | 858656-55-0

• 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: [Sm(N,N′-bis(2,6-diisopropylphenyl)formamidinate)2(tetrahydrofuran)2]
• 英文别名: [(N,N’-bis(2,6-diisopropylphenyl)formamidinate)₂Sm^II(tetrahydrofuran)₂]；[Sm(N,N′-bis(2,6-diisopropylphenyl)formamidinate)₂(tetrahydrofuran)₂]；[(N,N'-bis(2,6-diisopropylphenyl)formamidino)₂Sm(tetrahydrofuran)₂]；[Sm(N,N’-bis(2,6-diisopropylphenyl)formamidinate)₂(thf)₂]；[Sm(N,N′-bis(2,6-diisopropylphenyl)formamidinate)₂(thf)₂]；(N,N’-bis(2,6-diisopropylphenyl)formamidinate)₂Sm(thf)₂；[Sm(N,N′-2,6-diisopropylphenylformamidinate)₂(thf)₂]
• CAS: 858656-55-0
• 化学式: C₅₈H₈₆N₄O₂Sm
• 分子量: 1021.71
• InChiKey: JKMFWMORDZWFDG-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：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Sm(N,N′-bis(2,6-diisopropylphenyl)formamidinate)2(tetrahydrofuran)2] 在 二苯基汞 作用下， 以 甲苯 为溶剂， 生成 [Sm(N,N′-bis(2,6-diisopropylphenyl)formamidinate-κ²N,N')₂(tetrahydrofuran)(ethenolate)]
  参考文献：
  名称：

  Bulky Formamidinate-Supported Lanthanoid Halides and Alkyls, Including a Rare Terminal La–Me Species

  摘要：

  The oxidation of [Sm(DippForm)(2)(thf)(2)] (1; DippFormH = N,N'-bis(2,6-diisopropylphenyl)forrnamidine) by tert-butyl chloride, 1,2-dibromoethane, and iodine, respectively, at ambient temperature led to the isolation of the light yellow crystalline samarium(III) halide complexes [Sm(DippForm)(2)X(thf)] (2, X = Cl; 3, X = Br; 4, X = I) in good yield. The subsequent metathesis reaction of [Ln(DippForm)(2)X(thf)] (2, Ln = Sm, X = Cl; Ln = La, X = F) with LiMe and LiCH2SiMe3 generated the samarium alkyl complexes [Sm(DippForm)(2)R(thf)] (5, R = Me; 6, R = CH2SiMe3) and the rare terminal La-Me complex [La-(DippForm)(2)Me(thf)] (7). The attempted ligand exchange reaction of 7 with 1,2,3,4-tetraphenylcyclopentadiene gave, unexpectedly, the homoleptic tris-(formamidinato)lanthanum complex [La(DippForm)(3)] (8) in very low yield. The redox transmetalation/protolysis (RTP) reaction from samarium metal with bis(2-bromo-3,4,5,6-tetrafluorophenyl)mercury and DippFormH in thf yielded the mono(formamidinato)samarium(III) complex [Sm(DippForm)Br-2(thf)(3)] (9) as a coproduct with the bis(formamidinate) 3. Redox reaction of the divalent samarium complex [Sm(DippForm)(2)(thf)(2)] (1) with ciiphenylmercury resulted in the ethenolate complex [Sm(DippForm)(2)(OCH=CH2)(thf)] (10) instead of the target Sm-Ph complex, the product resulting from the decomposition of Lewis base thf molecules.

  DOI：

  10.1021/om301048b
• 作为产物：
  描述：

  [Sm(N,N′-bis(2,6-diisopropylphenyl)formamidinate-κ²N,N')₂(tetrahydrofuran)Cl] 在 potassium graphite 作用下， 以 氘代苯 为溶剂， 反应 0.02h， 生成 [Sm(N,N′-bis(2,6-diisopropylphenyl)formamidinate)2(tetrahydrofuran)2]
  参考文献：
  名称：

  具有C═O和C═S键的大甲Form（II或III）配合物的反应性

  摘要：

  讨论了一种新的异双金属sa（Ⅱ）甲酰胺化物配合物的制备以及selected（Ⅱ）配合物和一种sa（Ⅲ）甲酰胺配合物与二苯甲酮或CS 2的选择反应。三（formamidinato）钐的治疗（III）配合物[SM（DippForm）3 ] 1（DippForm = Ñ，Ñ ' -双（2,6-二异丙基）甲脒，（CH（NC 6 H ^ 3 -我镨2 - 2,6）2）与钾石墨在甲苯中制得暗褐色的异双金属甲酰胺基osa（II）/钾络合物[KSm（DippForm）3 ] n 2。如图2所示，无路易斯碱的无溶剂均质物种与相关的杂合甲酰胺基osa（II）配合物[Sm（DippForm）2（thf）2 ] 3的组成，结构和对二苯甲酮的反应性显着不同。当2反应生成络合物1时，3与二苯甲酮反应生成高度不寻常的[Sm（DippForm）2（thf）{μ-OC（Ph）═（C 6 H 5）C（Ph）2 O} Sm（DippForm

  DOI：

  10.1021/ic502181g

文献信息

• The synthesis of a sterically hindered samarium(ii) bis(amidinate) and conversion to its homoleptic trivalent congener
  作者：Marcus L. ColePresent address: Department of、Peter C. Junk

  DOI：10.1039/b501447f

  日期：——

  The first divalent samarium bis(amidinate) has been prepared and aspects of its novel chemistry, including the preparation of a sterically hindered homoleptic Sm(III) tris(amidinate), explored.

  首个二价二酰胺合钐化合物已被制备出来，并探索了其新颖化学性质，包括制备立体障碍型同多钐(III)三酰胺配合物。
• Exploring the effect of the Ln^III/Ln^IIredox potential on C–F activation and on oxidation of some lanthanoid organoamides
  作者：Glen B. Deacon、Peter C. Junk、Rory P. Kelly、Jun Wang

  DOI：10.1039/c5dt04239a

  日期：——

  in toluene at 110 °C for three days did not afford any samarium fluoride complex. An RTP reaction with Sm afforded the heteroleptic samarium complex, [Sm(LMe)2F]3, in very low yield. From an attempted protolysis reaction between [Sm(DippForm)2(thf)2] and LMeH, the mixed ligand samarium fluoride complex, [Sm(DippForm)(LMe)F]2, was isolated. Overall, the instability of SmII precludes control over the C–F

  二价euro络合物[Eu（L Me / Et）2（thf）2 ]和[Eu（L Et）2（dme）]（L Me / Et = p -HC 6 F 4 N（CH 2）2 NMe 2 / Et 2），是由Eu金属，Hg（C 6 F 5）2和L Me / Et H在thf中的氧化还原-金属转移/质子分解（RTP）反应制备的。配合物表现出紧密的（C）F–Ln相互作用，并且酰胺配体具有三齿N，N '，F螯合。配合物具有很强的热稳定性，但在暴露于光线下会发生CF活化。从[Eu（L Et）2（thf）2 ]暴露于光后，分离出Eu III混合氟化物/氧化物簇[Eu 4（L Et）6 F 2 O 2 ]，但其他定义明确的C–由于Eu II的稳定性，已证明F活化产物难以捉摸。用I 2氧化[Ln（L R）2（thf）2 ]（Ln = Eu，R = Me; Ln = Yb，R = Et）可以得到杂配碘配合物[Ln（L
• Reactivity of bulky Ln(<scp>ii</scp>) amidinates towards P₄, As₄, and As₄S₄
  作者：Christoph Schoo、Sebastian Bestgen、Ralf Köppe、Serygey N. Konchenko、Peter W. Roesky

  DOI：10.1039/c8cc01519h

  日期：——

  The reduction of P4, As4 and As4S4 (realgar) with the sterically encumbered reductants [(DippForm)2Ln(thf)2] (Ln = Sm, Yb; DippForm = (2,6-iPr2C6H3)NC(H) = N(2,6-iPr2C6H3)}−) is reported. For the first time, purely f-element containing inverse inorganic sandwich complexes [(DippForm)2Sm}2(μ2-η4:η4-E4)] (E = P, As), featuring a π-aromatic cyclo [E4]2− middle deck, were obtained upon reaction with

  P 4，As 4和As 4 S 4（雄黄）的还原是通过空间阻碍的还原剂[（DippForm）2 Ln（thf）2 ]（Ln = Sm，Yb; DippForm = （2,6- i Pr 2报告了C 6 H 3）NC（H）＝ N（2，6 - i Pr 2 C 6 H 3）} -）。首次，纯粹的f-元件含有逆无机夹心复合物[（DippForm）2钐} 2（μ 2 -η 4：η 4 -E 4）]（E = P，As），其特征在于，通过与P 4和As 4反应，得到了一个π-芳族环[E 4 ] 2−中间甲板。与雄黄的反应会导致笼子破裂，并形成异常物种[（DippForm）（DippForm-AsS 2）} Ln（thf）]。与茂金属相比，二价L酰胺对主族分子的反应性更快，更有效，因此受配体环境的影响很大。DFT计算支持实验结果。
• Bulky Ytterbium Formamidinates Stabilise Complexes with Radical Ligands, and Related Samarium “Tetracyclone” Chemistry
  作者：Daniel Werner、Xuefei Zhao、Stephen P. Best、Laurent Maron、Peter C. Junk、Glen B. Deacon

  DOI：10.1002/chem.201604203

  日期：2017.2.10

  further reduced to a dianion (1‐oxido‐2,3,4,5‐tetraphenylcyclopentadianide2−), (C5Ph4}‐O)2− by [SmI2(thf)2], giving dimeric [SmI(C5Ph4}‐O)(thf)2}2] (Sm11) and monomeric complexes [YbI(DippForm)2(thf)] (11 b) and [YbI2(DippForm)(thf)2] (11 c). Activated Sm metal reduced neutral tetracyclone to the dianion, (C5Ph4}‐O)2−, in THF, giving tetranuclear [SmII2(C5Ph4}‐O)2(thf)3}2] (Sm13). Treatment of Sm13

  二价[Yb（DippForm）2（thf）n ]（n = 2（1 a）或1（1 b），DippForm = N，N'-双（2,6-二异丙基苯基）甲ami酸酯）配合物用酮：9-芴酮（fn）或2,3,4,5-四苯基环戊二烯酮（tPC，四环酮），得到酮基络合物：[Yb（DippForm）2（fn . - O）（thf）]（2），和[镱（DippForm）2（TPC 。 - ø）]（3），分别为（羰游基=含有一个C自由基阴离子。 -O （ - ）团体。相比之下，当全氟二苯甲酮（pfb）用1 a或1 b处理时，短暂的酮基形成随后通过C-F活化途径快速分解，得到[YbF（DippForm）2（thf）]（4 a）和一种非常不寻常的氟化物/氧化物桥连物种：[Yb 5 F 6 O 2（DippForm）5 ]（4 b）。还检查了二酮的还原：3,5-二叔丁基1,2-苯醌（tbbq），9,10-菲醌（phen）或1
• Synthesis and reactivity of rare-earth metal phosphaethynolates
  作者：Sebastian Bestgen、Qien Chen、Nicholas H. Rees、Jose M. Goicoechea

  DOI：10.1039/c8dt03427c

  日期：——

  and reactivity of molecular metal phosphaketenes (M–PCO) has gained increasing attention. However, lanthanide complexes of the heavier group 15 cyanate analogue PCO− have not been investigated so far. Herein we present exemplar studies on the nature and reactivity of rare-earth phosphaethynolato-complexes using three characteristic representatives of the rare-earth metals: Y, Nd and Sm. Our investigations

  在过去的六年中，关于分子金属磷烯（M–PCO）的合成和反应性的研究受到越来越多的关注。然而，较重的15组氰酸模拟PCO的稀土配合物-尚未到目前为止调查。在此，我们使用稀土金属的三个特征代表：Y，Nd和Sm，对稀土磷乙炔络合物的性质和反应性进行示例性研究。我们的研究包括+2和+3氧化还原状态，以及一个定义的基于mid基的配体组，以及在螯合剂18-crown-6和2,2,2-crypt存在下的新型反应途径。