samarium diiodide bis(tetrahydrofuran) | 94138-28-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: samarium diiodide bis(tetrahydrofuran)
• 英文别名: SmI2(THF)2；SmI2(tetrahydrofuran)2；Smi2(thf)x；diiodosamarium;oxolane
• CAS: 94138-28-0
• 化学式: C₈H₁₆I₂O₂Sm
• 分子量: 548.383
• InChiKey: PZKXTGPAGLIYFP-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.37
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  samarium diiodide bis(tetrahydrofuran) 以 四氢呋喃 、 苯 为溶剂， 反应 12.5h， 生成
  参考文献：
  名称：

  Homoleptic Divalent Dialkyl Lanthanide-Catalyzed Cross-Dehydrocoupling of Silanes and Amines

  摘要：

  The rare-earth bis(alkyl) compound Sm{C(SiHMe2)(3)}(2)THF2 (1b) is prepared by the reaction of samarium(II) iodide and 2 equiv of KC(SiHMe2)(3). This synthesis is similar to that of previously reported Yb{C(SiHMe2)(3)}2THF(2) (la), and compounds la,b are isostructural. Reactions of lb and 1 or 2 equiv of B(C6F5)(3) afford SmC(SiHMe2)(3)HB(C6F5)(3)THF2 (2b) or Sm{HB(C6F5)(3)}2THF(2) (3b), respectively, and 1,3-disilacyclobutane {Me2Si-C(SiHMe2)(2)}(2) as a byproduct. Bands from 2300 to 2400 cm(-1) assigned to vBH in the IR spectra and highly paramagnetically shifted signals in the 1113 NMR spectra of 2b and 3b provided evidence for Sm-coordinated HB(C6F5)(3). Compounds la,b react with the bulky N-heterocyclic carbene (NHC) 1,3-di-tert-butylimidazol-2-ylidene (ImtBu) to displace both THF ligands and give three-coordinate monoadducts Ln{C(SiHMe2)(3)}(2)]mtBu (Ln = Yb (4a), Sm (4b)). Complexes 4a,b catalyze cross-dehydrocoupling of organosilanes with primary and secondary amines at room temperature to give silazanes and 112, whereas la,b are not effective catalysts under these conditions. Second-order plots of In{[Et2NH]/[Ph2SiH2]} vs time for 4a-catalyzed dehydrocoupling are linear and indicate first-order dependences on silane and amine concentrations. However, changes in the experimental rate law with increased silane concentration or decreased amine concentration reveal inhibition by silane. In addition, excess ImtBu or THF inhibit the reaction rate. These data, along with the structures of 4a,b, suggest that the bulky carbene favors low coordination numbers, which is important for accessing the catalytically active species.

  DOI：

  10.1021/acs.organomet.6b00138
• 作为产物：
  描述：

  四氢呋喃 、 三氢化钐 、 1,2-二碘乙烷 以71%的产率得到samarium diiodide bis(tetrahydrofuran)
  参考文献：
  名称：

  β-二酮亚胺 Sm II 配合物的合成及反应性

  摘要：

  用庞大的 β-二酮亚胺配体 HC[C(Me)=N(DIPP)] 2 (BDI) 稳定 Tm II金属中心的尝试失败了（DIPP，2,6-二异丙基苯基）。TmI 2和 2 equiv 的反应。(BDI)K 得到 Tm III复合物 (BDI)(BDI-H)Tm ( 1 )，其中 (BDI-H) 2-是双去质子化配体。然而，按照相同的路线，(BDI) 2 Sm ( 2 ) 以 48% 的结晶产率分离。配合物2高度溶于芳香族溶剂或烷烃，可与各种试剂如吩嗪、PhSSPh、O 2、NO、孜然和芴酮反应。这导致以下 Sm 的隔离和结构表征III配合物：[(BDI) 2 Sm] 2 (μ-吩嗪) ( 3 ), [(BDI)Sm(SPh)(μ-SPh)] 2 ( 4 ), (BDI)(BDI-H)Sm ( 5a )、(BDI) 2 Sm(OC 13 H 8 ) ( 6 ) 和 (BDI) 2 Sm(NO 2

  DOI：

  10.1071/ch21296
• 作为试剂：
  描述：

  tert-butyl((3,3-dimethylbut-1-en-2-yl)oxy)dimethylsilane 、 Acetic acid, [(4-methoxyphenyl)imino]-, ethyl ester, (2E)- 在 samarium diiodide bis(tetrahydrofuran) 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以30%的产率得到ethyl (Z)-4-[tert-butyl(dimethyl)silyl]oxy-2-(4-methoxyanilino)-5,5-dimethylhex-3-enoate
  参考文献：
  名称：

  镧系元素碘化物催化的串联反应。第2部分：串联亚氨基醇-烯醇化反应

  摘要：

  二碘化is是用于环状和无环叔丁基二甲基甲硅烷基烯氧基硅烷与螯合亚胺反应的催化剂。分离出反应产物为β-氨基烯氧基硅烷，而不是先前用相应的三甲基甲硅烷基环氧硅烷观察到的β-氨基酮。讨论了几种机械途径。

  DOI：

  10.1016/j.tet.2004.01.082

文献信息

• Isolation, X-ray Structural Characterization, and Reactivities of Diiodosamarium(II) Complexes Bearing Amide Compounds as Ligands
  作者：Masayoshi Nishiura、Kosuke Katagiri、Tsuneo Imamoto

  DOI：10.1246/bcsj.74.1417

  日期：2001.8

  The structures of diiodosamarium(II) complexes with amide compounds have been investigated basing on single crystal X-ray structural analyses. The reaction of [SmI2(thf)2] with 2 equivalents of tetramethylurea (TMU) gave [SmI2(thf)2(tmu)2] (1). The three different kinds of ligands in 1 attach to the samarium atom in a trans orientation. [SmI2(thf)2] reacted with 4 equivalents of 1,3-dimethyl-2-imidazolidione

  已经基于单晶 X 射线结构分析研究了二碘钐 (II) 与酰胺化合物的配合物的结构。[SmI2(thf)2]与2当量的四甲基脲(TMU)反应得到[SmI2(thf)2(tmu)2](1)。1 中的三种不同类型的配体以反式取向连接到钐原子。[SmI2(thf)2]与4当量的1,3-二甲基-2-咪唑啉酮(DMI)反应得到[SmI2(dmi)4](2)，形成典型的六配位八面体结构。含有四个 N,N-二甲基乙酰胺 (DMA) 配体 [SmI2(dma)4] (3) 的 Diiodosamarium 复合物是通过用 4 当量的 DMA 处理 [SmI2(thf)2] 来制备的。[SmI2(thf)2] 与 6 当量的 1,3-二甲基-3,4,5,6-四氢-2-(1H)-嘧啶酮（二甲基丙烯脲 (DMPU)）反应得到 [Sm(dmpu)6 ]I2 (4) 定量。该复合物具有独特的配位方式，其中六个 DMPU
• Fluorenyl andansa-Dimethylsilylbis(fluorenyl) Derivatives of Divalent Ytterbium and Samarium − Synthesis and Structure of the First Mixed-Ligand LnII Classic Sandwich Complex (C13H9)(C5Me5)Yb(DME)
  作者：Alexander A. Trifonov、Evgenii N. Kirillov、Sebastian Dechert、Herbert Schumann、Mikhail N. Bochkarev

  DOI：10.1002/1099-0682(200109)2001:10<2509::aid-ejic2509>3.0.co;2-f

  日期：2001.9

  (C13H9)YbI(DME) (5), but the redistribution products YbI2(DME) and 2. The first mixed-ligand sandwich complex of a divalent lanthanide metal (C13H9)(C5Me5)Yb(DME) (6) was prepared in a one-pot reaction of 4 with C5Me5H and C13H9K in DME. ansa-Me2Si(C13H8)2Yb(THF) (7) and ansa-Me2Si(C13H8)2Sm(THF)4 (8) were obtained by treatment of the appropriate LnII iodides with ansa-Me2Si(C13H9)2K2 in THF. The molecular

  二价镱 (C13H9)2Yb(L)n 的新型芴基配合物 [L = THF, n = 2 (1); L = DME, n = 1 (2)] 已通过 YbI2(THF)2 与 2 当量的反应制备。C13H9K 以及 (C10H8)Yb(THF)2 与芴在 THF 中的反应。tBuN=CHCH=NtBu (DAD) 对 1 的氧化导致 (C13H9)2Yb(DAD) (3) 的形成。YbI(DME)2]2(μ-C10H8)} (4) 与芴的反应没有得到 (C13H9)YbI(DME) (5)，而是重新分配产物 YbI2(DME) 和 2。第一个混合二价镧系元素金属 (C13H9)(C5Me5)Yb(DME) (6) 的配体夹心络合物是在 4 与 C5Me5H 和 C13H9K 在 DME 中的一锅反应中制备的。ansa-Me2Si(C13H8)2Yb(THF) (7) 和 ansa-Me2Si(C13H8)2Sm(THF)4
• Activation of Ene-Diamido Samarium Methoxide with Hydrosilane for Selectively Catalytic Hydrosilylation of Alkenes and Polymerization of Styrene: an Experimental and Theoretical Mechanistic Study
  作者：Jianfeng Li、Chaoyue Zhao、Jinxi Liu、Hanmin Huang、Fengxin Wang、Xiufang Xu、Chunming Cui

  DOI：10.1021/acs.inorgchem.6b01670

  日期：2016.9.6

  syndiospecific polymerization of styrene upon activation with phenylsilane and regioselective hydrosilylation of styrenes and nonactivated terminal alkenes. Unprecedented regioselectivity (>99.0%) for both types of alkenes has been achieved with the formation of Markovnikov and anti-Markovnikov products in high yields, respectively, whereas the polymerization of styrene resulted in the formation of syndiotactic

  掺有烯二酰胺配体L（DME）Sm（μ-OMe）2 Sm（DME）L（1 ; L = [DipNC（Me）C（Me）NDip] 2–的二甲基，Dip = 2,6- i（Pr 2 C 6 H 3和DME ＝ 1，2-二甲氧基乙烷）已经被制备并在结构上表征。综合大楼1苯硅烷活化和苯乙烯与非活​​化末端烯烃的区域选择性氢化硅烷化反应催化苯乙烯的间同特异性聚合。分别以高收率形成Markovnikov和抗Markovnikov产物，实现了两种烯烃前所未有的区域选择性（> 99.0％），而苯乙烯的聚合导致间同立构的甲硅烷基封端的低聚苯乙烯的形成。动力学实验和密度泛函理论计算有力地支持了由Sm–OMe键1与PhSiH 3的σ键复分解生成的氢化mar中间体。。另外，观察到的用于氢化硅烷化和聚合的区域选择性与计算的能量分布一致，这表明庞大的烯-二叠氮配体和氢化sa中间体对于区域和立体选择性具有重要作用。
• Synthesis and Structures ofcisoidandtransoidBis(1,2-dimethoxyethane)bis(η2-pyrazolato)lanthanoid(II) Complexes
  作者：Glen B. Deacon、Ewan E. Delbridge、Brian W. Skelton、Allan H. White

  DOI：10.1002/(sici)1099-0682(199905)1999:5<751::aid-ejic751>3.0.co;2-5

  日期：1999.5

  The complexes [Yb(bind)2(DME)2], [Yb(MePhpz)2(DME)2], [Yb(azin)2(DME)2], and [Eu(Ph2pz)2(DME)2] (bindH = 4,5-dihydro-2H-benz[g]indazole; MePhpzH = 3-methyl-5-phenylpyrazole; azinH = 7-azaindole; Ph2pzH = 3,5-diphenylpyrazole; DME = 1,2-dimethoxyethane) have been prepared by redox transmetallation between ytterbium or europium metal and the corresponding thallium(I) pyrazolate in tetrahydrofuran (THF)

  配合物 [Yb(bind)2(DME)2]、[Yb(MePhpz)2(DME)2]、[Yb(azin)2(DME)2] 和 [Eu(Ph2pz)2(DME)2] （bindH = 4,5-二氢-2H-苯并[g]吲唑；MePhpzH = 3-甲基-5-苯基吡唑；azinH = 7-氮杂吲哚；Ph2pzH = 3,5-二苯基吡唑；DME = 1,2-二甲氧基乙烷）在金属汞的存在下，通过镱或铕金属与相应的吡唑铊（I）在四氢呋喃（THF）中的氧化还原金属转移反应制备，然后用 DME 处理。铊试剂是通过用乙醇铊（I）处理合适的吡唑而获得的。[Yb(Ph2pz)2(DME)2]和[Sm(Ph2pz)2(DME)2]均由LnI2(THF)2和K(Ph2pz)在THF中复分解制备，而前者也已获得通过 [Hg(Ph2pz)2] 和镱金属的氧化还原金属转移以及 3,5-二苯基吡唑与 Yb(C6F5)2 的反应，后者来自
• Synthesis of homometallic divalent lanthanide organoimides from benzyl complexes
  作者：Benjamin M. Wolf、Christoph Stuhl、Reiner Anwander

  DOI：10.1039/c8cc05234d

  日期：——

  The reaction of LnI2(thf)2 with benzyl potassium affords the homoleptic benzyl complexes [Ln(CH2Ph)2]n of samarium, europium, and ytterbium. In the cases of Eu and Yb, the treatment of [Ln(CH2Ph)2]n with one equivalent of 2,6-diisopropylaniline gives access to tetrameric organoimide complexes [(thf)Ln(μ3-NDipp)]4, representing the first examples of homometallic Ln(II) imides. This study revealed that

  LnI 2（thf）2与苄基钾的反应提供了,、 euro和的均质苄基配合物[Ln（CH 2 Ph）2 ] n。在Eu和Yb组成的情况下，治疗[LN（CH 2 PH）2 ] Ñ与一个当量的2,6-二异丙基苯胺的可以访问的四聚体复合物organoimide [（THF）LN（μ 3 -NDipp）] 4，代表均金属的Ln（II）酰亚胺的第一个实例。这项研究表明，Yb（II）有机酰亚胺的化学性质与钙的化学性质显着不同。