tris(pentamethylcyclopentadienyl)uranium(III) | 190076-36-9

• 英文名称: tris(pentamethylcyclopentadienyl)uranium(III)
• 英文别名: uranium tris(pentamethylcyclopentadienyl)；(pentamethylcyclopentadienyl)3(uranium)；(C5Me5)3 uranium(III)；[(η5-C5Me5)3U]；(C5Me5)3U
• CAS: 190076-36-9
• 化学式: C₃₀H₄₅U
• 分子量: 643.716
• InChiKey: YRFTWKOOWKOZOO-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：

  tris(pentamethylcyclopentadienyl)uranium(III) 、 氘代苯 在 KC₈ 作用下， 以 氘代苯 为溶剂， 生成 [(C5Me5)2U]2(μ-η6:η6-C6H6)
  参考文献：
  名称：

  六电子还原剂 [(C5Me5)2U]2(μ-η6:η6-C6H6) 的结构、反应性和密度泛函理论分析，通过 (C5Me5)3M 反应性的新模式合成

  摘要：

  空间拥挤的 (C(5)Me(5))(3)U 复合物与苯中的 KC(8) 或 K/(18-crown-6) 反应形成 [(C(5)Me(5))( 2)U](2)(mu-eta(6):eta(6)-C(6)H(6))、1和KC(5)Me(5)。这些反应表明 (C(5)Me(5))(3)U 可能容易受到 (C(5)Me(5))(1-) 苯阴离子通过离子盐复分解的取代。为了在更传统的产品的合成中测试这个想法，(C(5)Me(5))(3)U 用 KN(SiMe(3))(2) 处理形成 (C(5)Me(5) ))(2)U[N(SiMe(3))(2)] 和 KC(5)Me(5)。1 具有与 (C(5)Me(5))(3)U 相当的长 UC(C(5)Me(5)) 键距，并且它也易受 (C(5)Me(5))( 1-) 通过离子复分解取代： 1 与 KN(SiMe(3))(2) 反应以使其酰胺取代类似物 [[(

  DOI：

  10.1021/ja0463886
• 作为产物：
  描述：

  以 氘代苯 为溶剂， 生成 tris(pentamethylcyclopentadienyl)uranium(III)
  参考文献：
  名称：

  A Monometallic f Element Complex of Dinitrogen:  (C₅Me₅)₃U(η-N₂)

  摘要：

  The reactivities of (C5Me5)3U and (C5Me4H)3U were compared using both common (THF) and nontraditional (N2) ligands for f elements. THF coordinates the less-crowded (C5Me4H)3U to form (C5Me4H)3U(THF) while ring opening occurs with sterically crowded (C5Me5)3U. N2 at 80 psi reacts with (C5Me5)3U to form (C5Me5)3U(eta1-N2) [U-N(N2) = 2.492(10) A, nu(N2) = 2207 cm-1, and cnt-U-N2 = 90 degrees ], whereas only (C5Me4H)3U was isolated under 80 psi of N2.

  DOI：

  10.1021/ja037647e

文献信息

• Multiple Syntheses of (C₅Me₅)₃U
  作者：William J. Evans、Gregory W. Nyce、Kevin J. Forrestal、Joseph W. Ziller

  DOI：10.1021/om010831t

  日期：2002.3.1

  sterically crowded (C5Me5)3U complex have been developed. (C5Me5)3U can be prepared by (a) reaction of [(C5Me5)2UH2]2with tetramethylfulvene, (b) reduction of (C5Me5)2Pb with (C5Me5)2UH(DMPE), (c) reaction of [(C5Me5)2U(L)]+ (L = THF, DMPE) with K(18-crown-6)(C5Me5), and (d) reaction of [(C5Me5)2U][BPh4] with KC5Me5. Reaction of (C5Me5)2UH(DMPE) with C8H8 forms the product of the (C5Me5)3U/C8H8 reaction

  已经开发了几种新的合成途径，可以达到空间拥挤的（C 5 Me 5）3 U配合物。（C 5我5）3 U可以通过[（C（a）的反应而制备的5我5）2 UH 2 ] 2与tetramethylfulvene，（B）还原（C的5我5）2与（C铅5我5）2 UH（DMPE），（c）[（C 5 Me 5）2 U（L）] +（L = THF，DMPE）与K（18-crown-6）（C5 Me 5），和（d）[（C 5 Me 5）2 U] [BPh 4 ]与KC 5 Me 5的反应。（C 5 Me 5）2 UH（DMPE）与C 8 H 8的反应形成了（C 5 Me 5）3 U / C 8 H 8反应的产物，[（C 8 H 8）（C 5 Me 5 ] U] 2（C 8 H 8）。（C的X射线晶体结构报告了本研究中使用的5 Me 5）2 U [N（SiMe 3）2 ]和[（C 5 Me 5）2 U] [BPh
• Comparative Reactivity of Sterically Crowded nf³ (C₅Me₅)₃Nd and (C₅Me₅)₃U Complexes with CO:  Formation of a Nonclassical Carbonium Ion versus an f Element Metal Carbonyl Complex
  作者：William J. Evans、Stosh A. Kozimor、Gregory W. Nyce、Joseph W. Ziller

  DOI：10.1021/ja036631l

  日期：2003.11.1

  compounds which have unconventionally long metal ligand distances, are found to react very differently with CO as a substrate. The 4f(3) complex (C(5)Me(5))(3)Nd reacts with CO to form a nonclassical carbonium ion complex, (C(5)Me(5))(2)Nd(O(2)C(7)Me(5)), which contains a three-coordinate planar carbon. (C(5)Me(5))(3)U reacts with CO to form an even more crowded CO adduct through a reaction type never

  发现空间拥挤的等电子 nf(3) (C(5)Me(5))(3)M 配合物的钕和铀，具有非常规长金属配体距离的化合物，与作为底物的 CO 反应非常不同。4f(3) 络合物 (C(5)Me(5))(3)Nd 与 CO 反应形成非经典的碳正离子络合物，(C(5)Me(5))(2)Nd(O(2) C(7)Me(5))，包含一个三配位平面碳。(C(5)Me(5))(3)U 与 CO 反应形成更加拥挤的 CO 加合物，其反应类型以前从未在 (C(5)Me(5))(3)M 化合物中观察到。稀有的铀羰基复合物 (C(5)Me(5))(3)U(CO) 的 nu(CO) = 1922 cm(-1) 和 UC(CO) 距离为 2.485(9) A。
• Sigma bond metathesis with pentamethylcyclopentadienyl ligands in sterically crowded (C5Me5)3M complexes
  作者：Thomas J. Mueller、Joseph W. Ziller、William J. Evans

  DOI：10.1039/c002654a

  日期：——

  reactions with (C5Me5)3Ce and (C5Me5)3U gave a mixture of C5Me5SPh and (C5Me5)2 as byproducts. PhSSPh reactions with the lanthanide nitrile adducts, (C5Me5)3Ln(NCCMe3)2 (Ln = La, Ce) and (C5Me5)3Nd(NCCMe3), formed [(C5Me5)2Ln(SPh)(NCCMe3)]2 and only C5Me5SPh as the byproduct. PhSeSePh reactions paralleled the PhSSPh results, but reactions of PhTeTePh with (C5Me5)3La, (C5Me5)3Sm, and (C5Me5)3La(NCCMe3)2

  为了进一步探索（C 5 Me 5）-配体在空间拥挤的（C 5 Me 5）3 M配合物中的反应性，与博士 （E = S， 硒， 特）已检查。与M =啦啦， 镨， 钕， m， 和 ÿ， 物理化学反应形成预期的还原产物[（C 5 Me 5）2 M（SPh）] 2，但主要的有机副产物不是空间诱导的还原产物（C 5 Me 5）2。相反，sigma键易位产物C 5 Me 5 SPh是主要的副产物。相反，与（C 5 Me 5）3 Ce和（C 5 Me 5）3 U的反应得到C 5 Me 5 SPh和（C 5 Me 5）2的混合物 作为副产品。 物理化学与镧系元素腈加合物（C 5 Me 5）3 Ln（NCCMe 3）2（Ln =啦啦， 铈）和（C 5 Me 5）3 Nd（NCCMe 3），形成[（C 5 Me 5）2 Ln（SPh）（NCCMe 3）] 2，仅形成C 5 Me 5 SPh作为副产物。硒化硒 反应与PhSSPh结果平行，但
• [(C5Me5)2U][(µ-Ph)2BPh2] as a four electron reductant
  作者：William J. Evans、Stosh A. Kozimor、Joseph W. Ziller

  DOI：10.1039/b508612d

  日期：——

  Examination of the reactivity of [(C5Me5)2U][(μ-Ph)2BPh2] as a “blank” for comparison with the four- and eight-electron reductive chemistry of the sterically crowded (C5Me5)3U and [(C5Me5)2U]2(C6H6) complexes revealed that the tetraphenylborate complex surprisingly functions as a four-electron reductant by combining [BPh4]1− and U(III) reduction; all three complexes cleave the NN bond in PhNNPh to form the bis(organoimido) U(VI) complex, (C5Me5)2U(NPh)2, and they also reduce PhCCPh to form (C5Me5)2U(C4Ph4).

  检查 [(C5Me5)2U][(μ-Ph)2BPh2] 作为“空白”的反应性，与空间拥挤的 (C5Me5)3U 和 [( C5Me5)2U]2(C6H6) 络合物揭示了四苯硼酸盐络合物通过结合 [BPh4]1- 和 U(III) 还原而令人惊讶地充当四电子还原剂；所有三种配合物都会裂解 PhNNPh 中的 NN 键，形成双（有机亚胺基）U(VI) 配合物 (C5Me5)2U(NPh)2，并且它们还会还原 PhCCPh 形成 (C5Me5)2U(C4Ph4)。
• Defining Reactivity Differences in Sterically Crowded (η⁵-C₅Me₅)₃M Complexes Based on Metal Size and Lanthanide vs Actinide Effects
  作者：Thomas J. Mueller、Gregory W. Nyce、William J. Evans

  DOI：10.1021/om101149z

  日期：2011.3.14

  Reactions between (eta(5)-C5Me5)(3)M and (eta(5)-O5Me5)(2)M'(mu-Ph)(2)BPh2 (M, M' = La, Ce, Pr, Nd, Sm, and U; M radius < M' radius) were examined to evaluate the relative steric crowding in the (C5Me5)(3)M series as a function of metal size and 4f vs 5f electron configuration. The sterically more crowded (C5Me5)(3)M complexes transfer (C5Me5)(-) to (C5Me5)(2)M'(mu-Ph)(2)BPh2 to generate less crowded (C5Me5)(3)M' products and (C5Me5)(2)M(mu-Ph)(2)BPh2 in mixtures with equilibrium constants in the range that allows all four components to be observed by NMR spectroscopy. The (C5Me5)(3)M to (C5Me5)(3)M' ratios depend on the difference in size of the two metals. Hence, (C5Me5)(3)Sm and (C5Me5)(2)La(mu-Ph)(2)BPh2 form a mixture with 99% (C5Me5)(3)La and 1% (C5Me5)(3)Sm, but the analogous reaction with (C5Me5)(2)Nd(mu-Ph)(2)BPh2 contains 90% (C5Me5)(3)Nd and 10% (C5Me5)(3)Sm. In analogous reactions with (C5Me5)(2)U(mu-Ph)(2)BPh2 and (C5Me5)(3)Ln lanthanide complexes, a size dependence is also observed, but the (C5Me5)3Ln complexes are favored over (C5Me5)(3)U to a greater extent than expected based on size differences.