[uranium(III)(1,2,3,4,5-pentamethylcyclopentadienide)2(2,2'-bipyridine)] | 874285-96-8

• 英文名称: [uranium(III)(1,2,3,4,5-pentamethylcyclopentadienide)2(2,2'-bipyridine)]
• CAS: 874285-96-8
• 化学式: C₃₀H₃₈N₂U
• 分子量: 664.674
• InChiKey: YKFKPFYOQUHDHS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [uranium(III)(1,2,3,4,5-pentamethylcyclopentadienide)2(2,2'-bipyridine)] 、 二苯甲酮吖嗪 以 甲苯 为溶剂， 以92%的产率得到(η5-C5Me5)2U(N=CPh2)2
  参考文献：
  名称：

  Small-Molecule Activation Mediated by a Uranium Bipyridyl Metallocene

  摘要：

  Addition of potassium graphite (KC8) to a solution of (eta(5)-C5Me5)(2)UCl2 (1) and 2,2'-bipyridine (bipy) gives the uranium bipyridyl metallocene (eta(5)-C5Me5)(2)U(bipy) (2) in good yield. In complex 2 a bipy radical anion is coordinated to a U(III) atom, and it is therefore an ideal starting material for small-molecule activation: e.g., it serves as a synthetic equivalent for the (eta(5)-C5Me5)(2)U-II fragment on treatment with conjugated alkynes and a variety of heterounsaturated molecules such as imines, carbodiimide, organic azides, hydrazine, and azo derivatives. Alternatively, it may also react with aldehydes, ketones, nitriles, and alpha,beta-unsaturated reagents such as p-ClPhCHO, (CH2)(5)CO, PhCN, and methyl methacrylate (MMA), forming the C-C bond coupling products (eta(5)-C5Me5)(2)U[(bipy) (p-ClPhCHO)] (10), (eta(5)-C5Me5)(2)U[bipy){(CH2)(5)CO}] (11), (eta(5)-C5Me5)(2)U[bipy)(PhCN)] (12), (eta(5)-C5Me5)(2)U[(bipy)CH2=C(Me)CO(OMe)] (13a), and {(eta(5)-C5Me5)(2)U{OC(OMe)=C(Me)CH2-3-bipy}](2) (13b), respectively, in quantitative conversion. Furthermore, addition of CuI to complex 2 induces a single -electron -transfer process to form the uranium(III) iodide complex (eta(5)-C5Me5)(2)U(I)(bipy) (14).

  DOI：

  10.1021/acs.organomet.7b00064
• 作为产物：
  描述：

  2,2'-联吡啶 、 (η⁵-C₅Me₅)₂U[η⁴-C₄(SiMe₃)₂] 以 氘代苯 为溶剂， 生成 [uranium(III)(1,2,3,4,5-pentamethylcyclopentadienide)2(2,2'-bipyridine)]
  参考文献：
  名称：

  Experimental and Computational Studies of a Uranium Metallacyclocumulene

  摘要：

  The synthesis, electronic structure, and reactivity of a uranium metallacyclocumulene were studied. Reduction of [(eta(5)-C5Me5)(2)UCl2] (1) with potassium graphite (KC8) in the presence of 1,4-bis(trimethylsilyl)butadiyne (Me3SiC=C-C=CSiMe3) forms the uranium metallacyclocumulene [(eta(5)-C5Me5)(2)U{eta(4)-C-4(SiMe3)(2)}] (2) in good yield. Magnetic susceptibility data confirm that 2 behaves as a U(IV) complex, and density functional theory (DFT) studies indicate a substantial 5f orbital contribution to the bonding of the metallacyclopentatriene U(eta(4)-C-C-C-C) moiety, leading to more covalent bonds between the [(eta(5)-C5Me5)(2)U](2+) and [eta(4)-C-4(SiMe3)(2)](2-) fragments than those found in the related Th(IV) compound. Consequently, very different reactivity patterns emerge; e.g., 2 can act as a synthetic equivalent for the (eta(5)-C5Me5)(2)U(II) fragment when reacted with conjugated species such as butadiyne, bipy, and diazabutadiene derivatives. Alternatively, the [(eta(4)-Me3SiC-C-C-CSiMe3)](2-) moiety in 2 may react as a nucleophile when exposed to a variety of simple heterounsaturated molecules such as aldehydes, ketones, nitriles, isothiocyanates, carbodiimides, pyridines, and organic azides. DFT studies are included to complement the experimental observations.

  DOI：

  10.1021/acs.organomet.6b00936

文献信息

• (η⁵-C₅Me₅)₂U(=P-2,4,6-^<i>t</i>Bu₃C₆H₂)(OPMe₃) Revisited—Its Intrinsic Reactivity toward Small Organic Molecules
  作者：Deqiang Wang、Guohua Hou、Guofu Zi、Marc D. Walter

  DOI：10.1021/acs.organomet.0c00640

  日期：2020.11.23

  alkynes RC≡CC≡CR, forming the disulfido compound (η5-C5Me5)2U(SPh)2 (5), diselenido compound (η5-C5Me5)2U(SePh)2 (6), bipy compound (η5-C5Me5)2U(bipy) (8), diiminato compound (η5-C5Me5)2U(N═CPh2)2 (9) and the metallacyclopentatrienes (η5-C5Me5)2U[η4-C4(R)2] (R = Ph (10), Me3Si (11)), respectively. Furthermore, compound 2 may also straightforwardly react with terminal alkynes and a variety of heterounsaturated

  路易斯碱稳定化的铀亚膦（η 5 -C 5我5）2 U（═P-2,4,6-吨卜3 c ^ 6 ħ 2）（OPME 3）（2），将其从（η衍生5 -C 5 Me 5）2 U（Cl）Me（1）和2,4,6-（Me 3 C）3 C 6 H 2在甲苯中Me 3的存在下的PHKPO最初是在1996年报道的，但是从那时起，它对有机小分子的反应性尚未得到广泛的研究。这种贡献弥合了这个差距，并且在配合物2向（小的）有机底物的反应中建立了不同的反应模式。例如，复杂的2可以释放亚膦部分（2,4,6-吨卜3 c ^ 6 ħ 2 P :)，并因此可作为（η的源极充当5 -C 5我5）2 ü II片段在Ph 2 S 2，Ph 2 Se 2的存在，联吡啶，酮连氮（PH 2 C = N）2，和共轭炔RC≡CC≡CR，形成disulfido化合物（η 5 -C 5我5）2 U（SPH）2（5），diselenido化合物（η
• Reductive heterocoupling mediated by Cp*₂U(2,2′-bpy)
  作者：Adil Mohammad、Dennis P. Cladis、William P. Forrest、Phillip E. Fanwick、Suzanne C. Bart

  DOI：10.1039/c2cc16200h

  日期：——

  Trivalent Cp*2U(2,2′-bpy) (2) (Cp* = C5Me5, 2,2′-bpy = 2,2′-bipyridine), which has a monoanionic bipyridine, was treated with p-tolualdehyde (a), furfuraldehyde (b), acetone (c), and benzophenone (d). Reduction of the CO bond followed by radical coupling with bipyridine forms the U(IV) derivatives [Cp*2U(2,2′-bpy)(OCRR′)] (3a–d).

  三价 Cp*2U(2,2â²-bpy)(2)（Cp* = C5Me5，2,2â²-bpy = 2,2â²-联吡啶）具有单阴离子联吡啶，用对甲苯醛 (a)、糠醛 (b)、丙酮 (c) 和二苯甲酮 (d) 处理。CO 键被还原，然后与联吡啶发生自由基偶联，形成 U(IV)衍生物[Cp*2U(2,2â²-bpy)(OCRRâ²)]（3aâd）。