dimethylbis(η5-pentamethylcyclopentadienyl)uranium | 67605-92-9

• 英文名称: dimethylbis(η5-pentamethylcyclopentadienyl)uranium
• 英文别名: bis(pentamethylcyclopentadienyl)-dimethyl-uranium(IV)；(C₅Me₅)₂U(Me)₂；(C₅Me₅)₂UMe₂；U(pentamethylcyclopentadienyl)₂Me₂；Cp*₂U(Me)₂；Cp*2UMe2
• CAS: 67605-92-9
• 化学式: C₂₂H₃₆U
• 分子量: 538.557
• InChiKey: SQXRPKCPBXWSFU-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：

  dimethylbis(η5-pentamethylcyclopentadienyl)uranium 以 二氯甲烷 、 甲苯 为溶剂， 生成 [(C₅Me₅)₂U(H)(μ-H)]₂
  参考文献：
  名称：

  Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds

  摘要：

  DOI：

  10.1021/ja00412a021
• 作为产物：
  描述：

  [(pentamethylcyclopentadienyl)2UMe][MeBPh3] 在 LiCH(Si(CH₃)3)2 or KN(Si(CH₃)3)2 作用下， 以 not given 为溶剂， 生成 dimethylbis(η5-pentamethylcyclopentadienyl)uranium
  参考文献：
  名称：

  Synthesis of (C₅Me₅)₂(C₅Me₄H)UMe, (C₅Me₅)₂(C₅H₅)UMe, and (C₅Me₅)₂UMe[CH(SiMe₃)₂] from Cationic Metallocenes for the Evaluation of Sterically Induced Reduction

  摘要：

  To probe the correlation of unusual (C5Me5)(1-) reactivity with steric crowding in complexes such as (C5Me5)(3)UMe and (C5Me5)(3)UCl, slightly less crowded (C5Me5)(2)(C5Me4H)UX analogues (X = Me, Cl) were synthesized and their reactivity was evaluated. The utility of the cationic precursors [(C5Me5)(2)UMe](1+), 1, and [(C5Me5)(2)UCl](1+), 2, in the synthesis of (C5Me5)(2)(C5Me4H)UMe, 3, and (C5Me5)(2)(C5Me4H)UCl, 4, was also explored. Since the use of precursor ((C5Me5)(2)UMe][MeBPh3], 1a, is complicated by the equilibrium between la and (C5Me5)(2)UMe2/BPh3, the reactivity of [(C5Me5)(2)UMe(OTf)](2), 1b, (OTf = O3SCF3) prepared from (C5Me5)(2)UMe2 and AgOTf, was also studied. Both 1a and 1b react with KC5Me4H to form 3. Complex 4 readily forms by addition of KC5Me4H to [(C5Me5)(2)UCl][MeBPh3], generated in situ from (C5Me5)(2)UMeCl and BPh3. Complex 1b was preferred to la for the synthesis of (C5Me5)(2)(C5H5)UMe, 5, and (C5Me5)(2)UMe[CH(SiMe3)(2)], 6, from KC5H5 and LiCH(SiMe3)(2), respectively. Complex 6 is the first example of a mixed alkyl uranium metallocene complex. Sterically induced reduction (SIR) reactivity was not observed with 3-6 although the methyl displacements from the (C5Me5)(1-) ring plane for 3 are the closest observed to date to those of SIR-active complexes. The H-1 NMR spectra of 3 and 4 are unusual in that all of the (C5Me4H)(1-) methyl groups are inequivalent. This structural rigidity is consistent with density-functional theory calculations.

  DOI：

  10.1021/ic801232e
• 作为试剂：
  描述：

  二甲胺基甲硼烷 在 dimethylbis(η5-pentamethylcyclopentadienyl)uranium 作用下， 以 氘代苯 为溶剂， 生成 tetramethyl-1,3-diborazane 、 cyclic(dimethylamino borane) dimer
  参考文献：
  名称：

  高活性Thor和铀茂金属配合物对二甲胺硼烷的催化脱氢

  摘要：

  and和铀络合物（C 5 Me 5）2 AnMe 2，[（C 5 Me 5）2 An（H）（μ-H）] 2（An = Th，U）和[（C 5 Me 5）2 U（H）] 2在室温下脱氢二甲胺硼烷（Me 2 NH·BH 3）。在45°C的温和加热下，可获得400 h –1的周转频率（TOFs），这与某些最快的Me 2 NH·BH 3相当脱氢催化剂在文献中是已知的。用于脱氢阿β-氢消除机构的因我的观察提出了2 N═BH 2中，Me 2 N═BMe 2和Me 2 N═BHMe在11催化和化学计量反应的乙NMR光谱。Me系元素二甲基和氢化物配合物与Me 2 NH·BH 3的相似催化指标表明，act系化合物氢化物是该化学反应中的活性催化剂。

  DOI：

  10.1021/acscatal.7b00967

文献信息

• Organoactinide phosphine/phosphite coordination chemistry. Facile hydride-induced dealkoxylation and the formation of actinide phosphinidene complexes
  作者：Michael R. Duttera、Victor W. Day、Tobin J. Marks

  DOI：10.1021/ja00322a028

  日期：1984.5

  A study of the reaction of the organoactinide hydrides (Cp'/sub 2/MH/sub 2/)/sub 2/ (Cp' = eta/sup 5/-(CH/sub 3/)/sub 5/C/sub 5/, M = Th, U) with trimethyl phosphite is reported. Quantitative transposition of hydride and methoxide ligands occurs to yield the corresponding Cp'/sub 2/M(OCH/sub 3/)/sub 2/ complexes (synthesized independently from Cp'/sub 2/MCl/sub 2/ and NaOCH/sub 3/) and the phosphinidene-bridged

  有机锕系氢化物反应的研究 (Cp'/sub 2/MH/sub 2/)/sub 2/ (Cp' = eta/sup 5/-(CH/sub 3/)/sub 5/C/sub 5/, M = Th, U) 与亚磷酸三甲酯报告。氢化物和甲醇盐配体发生定量转座以产生相应的 Cp'/sub 2/M(OCH/sub 3/)/sub 2/ 复合物（由 Cp'/sub 2/MCl/sub 2/ 和 NaOCH/sub 独立合成3/) 和膦亚基桥连的甲氧基复合物 (Cp'/sub 2/M(OCH/sub 3/))/sub 2/PH。M = U 的反应比 M = Th 的反应快得多。通过元素分析、/sup 1/H和/sup 31/P NMR、红外光谱、磁化率和D/sub 2/O水解对新化合物进行了表征。(Cp'/sub 2/U(OCH/sub 3/))/sub 2/PH 的分子结构已通过单晶 X 射线衍射技术确定。它在单斜空间群
• Uranium Metallocene Complexes of the 1,3,4,6,7,8-Hexahydro-2<i>H</i>-pyrimido[1,2-<i>a</i>]pyrimidinato Ligand, (hpp)⁻
  作者：William J. Evans、Elizabeth Montalvo、Joseph W. Ziller、Antonio G. DiPasquale、Arnold L. Rheingold

  DOI：10.1021/ic901790t

  日期：2010.1.4

  the azide complex, (C5Me5)2(hpp)UN3, 3. The trivalent uranium (hpp)− metallocene complex, (C5Me5)2(hpp)U, 4, can be synthesized by the reaction of [(C5Me5)2U][BPh4] with Khpp and from 2 with KC8. Complex 4 can be oxidized with Ph3P═Se to produce the tetravalent product, [(C5Me5)2(hpp)U]2(μ-Se), 5. The reaction of 4 with Me3SiN3 provides the pentavalent uranium complex, (C5Me5)2(hpp)U(=NSiMe3), 6

  通过合成茂金属配合物并对其进行研究，探讨了1,3,4,6,7,8-六氢-2 H-嘧啶并[1,2- a ]嘧啶基配体（hpp）-在铀化学中的用途。反应性。（C 5 Me 5）2 UMe 2与1当量的Hhpp反应形成（C 5 Me 5）2（hpp）UMe，1，它不再与Hhpp反应。（C 5我5）2 UCL 2种发生反应与Khpp到形式（C 5我5）2（HPP）UCL，2，同样不会与其他Khpp反应。复杂2分发生反应用的NaN 3，以形成叠氮化物复合物，（C 5我5）2（HPP）UN 3，3。三价铀（HPP）-茂金属配合物，（C 5我5）2（HPP）U，4，可通过以下的反应来合成的[（C 5我5）2 C] [BPH 4 ]与Khpp和从2用KC 8。配合物4可以被Ph 3氧化P═Se生成四价产物[（C 5 Me 5）2（hpp）U] 2（μ-Se），5。4与Me 3 SiN 3的反应提供了五价铀络合物（C
• A Mild Protocol To Generate Uranium(IV) Mixed-Ligand Metallocene Complexes using Copper(I) Iodide
  作者：Christopher R. Graves、Eric J. Schelter、Thibault Cantat、Brian L. Scott、Jaqueline L. Kiplinger

  DOI：10.1021/om800622g

  日期：2008.10.27

  (C5Me5)2U(O-2,6-iPr2-C6H3)(THF) (5) with copper(I) iodide affords the corresponding tetravalent uranium diiodide, amide iodide, and aryloxide iodide complexes (C5Me5)2UI2 (2), (C5Me5)2U[N(SiMe3)2](I) (6), (C5Me5)2U(NPh2)(I) (7) and (C5Me5)2U(O-2,6-iPr2-C6H3)(I) (8), respectively. This protocol was also extended to the synthesis of the alkyl iodide complex (C5Me5)2U(CHPh2)(I) (10). The isolation of complex 10

  三价铀络合物（C 5 Me 5）2 UI（THF）（1），（C 5 Me 5）2 U [N（SiMe 3）2 ]（3），（C 5 Me 5）2 U（ NPh 2）（THF）（4）和（C 5 Me 5）2 U（O-2,6- i Pr 2 -C 6 H 3）（THF）（5）与碘化铜（I）一起提供相应的四价铀二碘化物，酰胺碘化物和碘化芳基碘化物络合物（C 5 Me 5）2 UI 2（2），（C 5 Me 5）2 U [N（SiMe 3）2 ] （I）（6），（C 5 Me 5）2 U（NPh 2）（I）（7）和（C 5 Me 5）2 U（O-2,6- i Pr 2 -C 6 H 3） （一）（8）， 分别。该方案还扩展到烷基碘配合物（C 5 Me 5）2 U（CHPh 2）（I）（10）的合成。从原位生成的三价铀烷基络合物（C 5 Me 5）2 U（CHPh 2）（THF）（9）中分离出络合物1
• Catalystic activity of supported f-element organometallic complexes
  作者：Robert G. Bowman、Ryuichi Nakamura、Paul J. Fagan、Robert L. Burwell、Tobin J. Marks

  DOI：10.1039/c39810000257

  日期：——

  When supported on alumina, the organoactionoids M(η-Me5C5)2Me2(M = U or Th) exhibit very high catalytic activity for the hydrogenation of propene and the polymerization of ethene.

  当负载在氧化铝上时，有机活性类化合物M（η- Me 5 C 5）2 Me 2（M = U或Th）对丙烯的氢化和乙烯的聚合表现出非常高的催化活性。
• Synthesis, properties, and molecular structure of a trivalent organouranium diphosphine hydride
  作者：Michael R. Duttera、Paul J. Fagan、Tobin J. Marks、Victor W. Day

  DOI：10.1021/ja00367a045

  日期：1982.2

  Hydrogenolysis of U((CH/sub 3/)/sub 5/C/sub 5/)/sub 2/R/sub 2/, (R = CH/sub 3/Ch/sub 2/Si(CH/sub 3/)/sub 3/), proceeds at -20/sup 0/C in the presence of excess bis(2 dimethylphosphino)ethane(dmpe) according to this reaction: U((CH/sub 3/)/sub 3/C/sub 5/)/sub 2/R/sub 2/ + 1.5H/sub 2/ + dmpe ..-->.. (toluene, 18h) U((CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(dmpe) H + 2RH. Black microcrystals can be purified

  U((CH/sub 3/)/sub 5/C/sub 5/)/sub 2/R/sub 2/的氢解，(R = CH/sub 3/Ch/sub 2/Si(CH/sub 3) /)/sub 3/)，在过量双(2二甲基膦基)乙烷(dmpe)存在下在-20/sup 0/C下进行，根据该反应：U((CH/sub 3/)/sub 3/C /sub 5/)/sub 2/R/sub 2/ + 1.5H/sub 2/ + dmpe ..-->.. (甲苯, 18h) U((CH/sub 3/)/sub 5/C/ sub 5/)/sub 2/(dmpe) H + 2RH。黑色微晶可通过甲苯真空索氏萃取纯化。所有涉及该化合物的过程都必须在氩气或氦气气氛下进行，因为它会与氮气发生反应。通过NMR、红外光谱研究结构。摩尔磁化率在 295 K、5120 x 10/sup -4/emu 下测量，与 U (III) 公式一致