(pentamethylcyclopentadienyl)2U(=N-2,4,6-(t)Bu3C6H2) | 168557-93-5

• 英文名称: (pentamethylcyclopentadienyl)2U(=N-2,4,6-(t)Bu3C6H2)
• 英文别名: (pentamethylcyclopentadienyl)2U(N-2,4,6-tBu3-C6H2)；[(C5Me5)2U(N-2,4,6-tert-Bu3-C6H2)]
• CAS: 168557-93-5
• 化学式: C₃₈H₅₉NU
• 分子量: 767.922
• InChiKey: VRLKPMYUEGKQCS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  (pentamethylcyclopentadienyl)2U(=N-2,4,6-(t)Bu3C6H2) 在 N₂O 作用下， 以 甲苯 为溶剂， 以98%的产率得到
  参考文献：
  名称：

  Synthesis and Properties of High-Valent Organouranium Complexes Containing Terminal Organoimido and Oxo Functional Groups. A New Class of Organo-f-Element Complexes

  摘要：

  Monoimido derivatives of uranium(IV) have been prepared by both metathesis and direct protonation routes. The reaction of lithium anilide with (eta(5)-C(5)Me(5))(2)UMeCl in the presence of tetramethylethylenediamine (TMED) results in the isolation of the salt [Li(TMED)][eta(5)-C(5)Me(5))(2)U(NC6H5)Cl] (1). Compound 1 crystallizes in the space group P3(2), with unit cell dimensions a = 17.545(2) Angstrom, c = 9.407(2) Angstrom, V = 2507.8(7) Angstrom(3), Z = 3. Metathesis reactions with potassium anilide salts similarly result in the formation of monoimido chloride anionic derivatives of U(IV); these can be converted to neutral base adducts by reaction with the appropriate Lewis base at room temperature. A more direct route to the formation of neutral organoimido species with sterically encumbered aryl substituents is the reaction of (eta(5)-C(5)Me(5))(2)UMe(2) with 1 equiv H2NAr (Ar = 2,6-diisopropylphenyl or 2,4,6-tri-tert-butylphenyl). The base-free 2,6-diisopropyl derivative is highly soluble in all solvents, and the product of this protonation is best isolated as a base adduct, (eta(5)-C(5)Me(5))(2)U(N-2,6-i-Pr2C6H3)(THF) (6). The 2,4,6-tri-tert-butylphenylaniline product does not react further with tetrahydrofuran, however, and may be isolated as the base-free imido complex (eta(5)-C-5-Me(5))(2)U(N-2,4,6-t-Bu(3)C(6)H(2)) (8) Compound 8 crystallizes in the space group Pmn2(1), with unit cell dimensions a = 13.450(5) Angstrom, b = 12.138(5) Angstrom, c = 10.510(3) Angstrom, V = 1715.9(10) Angstrom(3), Z = 2. All of the organoimido compounds of uranium(IV) exhibit rich chemistry with two electron oxidative atom transfer reagents, providing an entirely new class of organouranium(VI) complexes containing terminal imido and oxo functional groups. Bis(imido) complexes such as (eta(5)-C(5)M(5))(2)U(NC6H5)(2) (3) can also be prepared by the unprecedented intramolecular reductive cleavage of 1,2-diphenylhydrazine at a uranium(IV) center. These complexes are in general surprisingly unreactive, but compound 3 will effect the unprecedented homolytic cleavage of dihydrogen to yield a bis(amide) derivative. The physical properties and chemical stability of these species suggests that significant uranium-imido and -oxo multiple bond character is present.

  DOI：

  10.1021/ja00142a011
• 作为产物：
  描述：

  dimethylbis(η5-pentamethylcyclopentadienyl)uranium 、 2,4,6-三叔丁基苯胺 以 甲苯 为溶剂， 以97%的产率得到(pentamethylcyclopentadienyl)2U(=N-2,4,6-(t)Bu3C6H2)
  参考文献：
  名称：

  Synthesis and Properties of High-Valent Organouranium Complexes Containing Terminal Organoimido and Oxo Functional Groups. A New Class of Organo-f-Element Complexes

  摘要：

  Monoimido derivatives of uranium(IV) have been prepared by both metathesis and direct protonation routes. The reaction of lithium anilide with (eta(5)-C(5)Me(5))(2)UMeCl in the presence of tetramethylethylenediamine (TMED) results in the isolation of the salt [Li(TMED)][eta(5)-C(5)Me(5))(2)U(NC6H5)Cl] (1). Compound 1 crystallizes in the space group P3(2), with unit cell dimensions a = 17.545(2) Angstrom, c = 9.407(2) Angstrom, V = 2507.8(7) Angstrom(3), Z = 3. Metathesis reactions with potassium anilide salts similarly result in the formation of monoimido chloride anionic derivatives of U(IV); these can be converted to neutral base adducts by reaction with the appropriate Lewis base at room temperature. A more direct route to the formation of neutral organoimido species with sterically encumbered aryl substituents is the reaction of (eta(5)-C(5)Me(5))(2)UMe(2) with 1 equiv H2NAr (Ar = 2,6-diisopropylphenyl or 2,4,6-tri-tert-butylphenyl). The base-free 2,6-diisopropyl derivative is highly soluble in all solvents, and the product of this protonation is best isolated as a base adduct, (eta(5)-C(5)Me(5))(2)U(N-2,6-i-Pr2C6H3)(THF) (6). The 2,4,6-tri-tert-butylphenylaniline product does not react further with tetrahydrofuran, however, and may be isolated as the base-free imido complex (eta(5)-C-5-Me(5))(2)U(N-2,4,6-t-Bu(3)C(6)H(2)) (8) Compound 8 crystallizes in the space group Pmn2(1), with unit cell dimensions a = 13.450(5) Angstrom, b = 12.138(5) Angstrom, c = 10.510(3) Angstrom, V = 1715.9(10) Angstrom(3), Z = 2. All of the organoimido compounds of uranium(IV) exhibit rich chemistry with two electron oxidative atom transfer reagents, providing an entirely new class of organouranium(VI) complexes containing terminal imido and oxo functional groups. Bis(imido) complexes such as (eta(5)-C(5)M(5))(2)U(NC6H5)(2) (3) can also be prepared by the unprecedented intramolecular reductive cleavage of 1,2-diphenylhydrazine at a uranium(IV) center. These complexes are in general surprisingly unreactive, but compound 3 will effect the unprecedented homolytic cleavage of dihydrogen to yield a bis(amide) derivative. The physical properties and chemical stability of these species suggests that significant uranium-imido and -oxo multiple bond character is present.

  DOI：

  10.1021/ja00142a011

文献信息

• Facile Access to Pentavalent Uranium Organometallics:  One-Electron Oxidation of Uranium(IV) Imido Complexes with Copper(I) Salts
  作者：Christopher R. Graves、Brian L. Scott、David E. Morris、Jaqueline L. Kiplinger

  DOI：10.1021/ja074889w

  日期：2007.10.1

  Uranium(V)−imido−iodide complexes have been prepared by chemical oxidation of the corresponding uranium(IV)−imido complexes with copper(I) iodide. These U(V) organometallic systems show reversible ...

  铀（V）-亚胺-碘化物配合物是通过相应的铀（IV）-亚胺配合物与碘化铜（I）的化学氧化制备的。这些 U(V) 有机金属系统显示出可逆的...
• Organometallic Uranium(V)−Imido Halide Complexes: From Synthesis to Electronic Structure and Bonding
  作者：Christopher R. Graves、Ping Yang、Stosh A. Kozimor、Anthony E. Vaughn、David L. Clark、Steven D. Conradson、Eric J. Schelter、Brian L. Scott、J. D. Thompson、P. Jeffrey Hay、David E. Morris、Jaqueline L. Kiplinger

  DOI：10.1021/ja711010h

  日期：2008.4.1

  Reaction of (C5Me5)2U(=N-2,4,6-(t)Bu3-C6H2) or (C5Me5)2U(=N-2,6-(i)Pr2-C6H3)(THF) with 5 equiv of CuX(n) (n = 1, X = Cl, Br, I; n = 2, X = F) affords the corresponding uranium(V)-imido halide complexes, (C5Me5)2U(=N-Ar)(X) (where Ar = 2,4,6-(t)Bu3-C6H2 and X = F (3), Cl (4), Br (5), I (6); Ar = 2,6-(i)Pr2-C6H3 and X = F (7), Cl (8), Br (9), I (10)), in good isolated yields of 75-89%. These compounds have

  (C5Me5)2U(=N-2,4,6-(t)Bu3-C6H2) 或 (C5Me5)2U(=N-2,6-(i)Pr2-C6H3)(THF) 与 5 当量的反应CuX(n) (n = 1, X = Cl, Br, I; n = 2, X = F) 提供相应的铀 (V)-亚胺卤化物络合物, (C5Me5)2U(=N-Ar)(X) （其中 Ar = 2,4,6-(t)Bu3- 和 X = F (3), Cl (4), Br (5), I (6); Ar = 2,6-(i)Pr2- 和 X = F (7), Cl (8), Br (9), I (10))，良好的分离产率为 75-89%。这些化合物的特点是结合了单晶 X 射线衍射、(1) H 核磁共振光谱、元素分析、质谱、循环伏安法、紫外-可见-近红外吸收光谱和变温磁化率。对 (C5Me5)2U(=N-2,4,6-(t)Bu3- )(Cl)
• Enhancing the reactivity of uranium(vi) organoimido complexes with diazoalkanesElectronic supplementary information (ESI) available: experimental, including general procedures, materials and synthesis of complexes 2 and 3. See http://www.rsc.org/suppdata/cc/b1/b109455f/
  作者：Jaqueline L. Kiplinger、David E. Morris、Brian L. Scott、Carol J. Burns

  DOI：10.1039/b109455f

  日期：2002.1.14

  two-electron oxidation of the uranium(IV) monoimido complex (C5Me5)2U(=N-2,4,6-t-Bu3C6H2) to give the uranium(VI) mixed bis(imido) complex, (C5Me5)2U(=N-2,4,6-t-Bu3C6H2)(=N-N=CPh2), which undergoes a rare cyclometallation reaction upon mild thermolysis to afford a uranium(IV) bis(amide) complex that results from net addition of a C-H bond of an ortho tert-butyl group across the N=U=N core.

  二苯基重氮甲烷对铀（IV）单亚胺基络合物（C5Me5）2U（= N-2,4,6-t-Bu3C6H2）进行双电子氧化，得到铀（VI）混合双（亚胺基）络合物（C5Me5） 2U（= N-2,4,6-t-Bu3C6H2）（= NN = CPh2），经温和热解后会进行罕见的环金属化反应，从而得到铀（IV）双（酰胺）络合物，该络合物是净添加N ＝ U ＝ N核上的邻叔丁基的CH键。