(pentamethylcyclopentadienyl)2[(Me)NNN(adamantyl)-κ2N,N(1,3)]UMe | 1160174-50-4

• 英文名称: (pentamethylcyclopentadienyl)2[(Me)NNN(adamantyl)-κ2N,N(1,3)]UMe
• 英文别名: [UMe(pentamethylcyclopentadienyl)2((Me)NNN(adamantyl)-κ2N(1,3))]
• CAS: 1160174-50-4
• 化学式: C₃₂H₅₁N₃U
• 分子量: 715.806
• InChiKey: FHAYDEWXCBKLJA-BRAHKJRLSA-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：
  None
• 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)2[(Me)NNN(adamantyl)-κ2N,N(1,3)]UMe 、 copper(I) bromide 以 甲苯 为溶剂， 以98%的产率得到(pentamethylcyclopentadienyl)2[(Me)NNN(adamantyl)-κ2N,N(1,3)]UBr
  参考文献：
  名称：

  Reactivity of Methyl Groups in Actinide Metallocene Amidinate and Triazenido Complexes with Silver and Copper Salts

  摘要：

  The effect of the heteroleptic ligand sets {(C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr]}(3-) and {(C(5)Me(5))(2)[(Me)-NNN(Ad)]}(3-) on actinide-carbon bond reactivity has been evaluated by examining the monomethyl actinide metallocene amidinate complexes (C(5)Me(5))(2)[(i)Pr-NC(Me)N(i)Pr-k(2)N,N']AnMe(An = U, 1; Th, 2) and the triazenido complex (C(5)Me(5))(2)[(Me)NNN(Ad)-k(2) N(1.3)]U Me, 3. This has led to a facile method to convert methyl groups in U(4+) and Th (4+) complexes to halide and pseudo-halide ligands. Complexes 1 and 3 react with AgOSO(2),CF(3) (AgOTf) to produce (C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-k(2) N,N(1)]U(OTf), 4, and (C(5)Me(5))(2)[(Mc)NNN(Ad)-k(2) N(1.3)]U(OTf), 5, respectively. The methyl complexes are also reactive with copper reagents, as demonstrated by the reactions of Cul with 1 and 2 to make(C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-k(2)N,N']UI,6, and(C(5)Me(5))2[(i)PrNC(Me)N(i)Pr-k(2) N,N']Th1,7, respectively. Similarly, reactions of CuBr with 1 and 3 generate (C(5)Me(5))2([)[(i)PrNC(Me)N(i)Pr-k(2)N,N']UBr, 8, and (C(5)MC(5))(2)[(Me)NNN(Ad)-K(2)N(1.3)] UBr, 9, respectively. These triflate and halide complexes are good precursors to other complexes with these ligand sets, as exemplified by their reactions with NaN(3), which produce (C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-k(2) N,N']U(N(3)), 10, and (C(5)Me(5))(2)[(Me)NNN(Ad)-k(2) N(1.3)]U(N(3)), 11, respectively. However, the reactions of 4 and 6 with LiCH(2)SiMe(3) lead to reduction and the formation of the trivalent uranium heteroleptic metallocene (C(5)Me(5))2[(i)PrNC(Me)N(i)Pr-k(2)-N,N']U, 12. LiCH(2)SiMe(3) does not cause reduction with the triazenido ligand set, and the monoalkyl complex (C(5)Me(5))(2)[(Me)NNN(Ad)-k(2)N(1.3)]U(CH(2)SiMe(3)), 13, can be isolated.

  DOI：

  10.1021/om9008179
• 作为产物：
  描述：

  dimethylbis(η5-pentamethylcyclopentadienyl)uranium 以 not given 为溶剂， 生成 (pentamethylcyclopentadienyl)2[(Me)NNN(adamantyl)-κ2N,N(1,3)]UMe
  参考文献：
  名称：

  Reactivity of Methyl Groups in Actinide Metallocene Amidinate and Triazenido Complexes with Silver and Copper Salts

  摘要：

  The effect of the heteroleptic ligand sets {(C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr]}(3-) and {(C(5)Me(5))(2)[(Me)-NNN(Ad)]}(3-) on actinide-carbon bond reactivity has been evaluated by examining the monomethyl actinide metallocene amidinate complexes (C(5)Me(5))(2)[(i)Pr-NC(Me)N(i)Pr-k(2)N,N']AnMe(An = U, 1; Th, 2) and the triazenido complex (C(5)Me(5))(2)[(Me)NNN(Ad)-k(2) N(1.3)]U Me, 3. This has led to a facile method to convert methyl groups in U(4+) and Th (4+) complexes to halide and pseudo-halide ligands. Complexes 1 and 3 react with AgOSO(2),CF(3) (AgOTf) to produce (C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-k(2) N,N(1)]U(OTf), 4, and (C(5)Me(5))(2)[(Mc)NNN(Ad)-k(2) N(1.3)]U(OTf), 5, respectively. The methyl complexes are also reactive with copper reagents, as demonstrated by the reactions of Cul with 1 and 2 to make(C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-k(2)N,N']UI,6, and(C(5)Me(5))2[(i)PrNC(Me)N(i)Pr-k(2) N,N']Th1,7, respectively. Similarly, reactions of CuBr with 1 and 3 generate (C(5)Me(5))2([)[(i)PrNC(Me)N(i)Pr-k(2)N,N']UBr, 8, and (C(5)MC(5))(2)[(Me)NNN(Ad)-K(2)N(1.3)] UBr, 9, respectively. These triflate and halide complexes are good precursors to other complexes with these ligand sets, as exemplified by their reactions with NaN(3), which produce (C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-k(2) N,N']U(N(3)), 10, and (C(5)Me(5))(2)[(Me)NNN(Ad)-k(2) N(1.3)]U(N(3)), 11, respectively. However, the reactions of 4 and 6 with LiCH(2)SiMe(3) lead to reduction and the formation of the trivalent uranium heteroleptic metallocene (C(5)Me(5))2[(i)PrNC(Me)N(i)Pr-k(2)-N,N']U, 12. LiCH(2)SiMe(3) does not cause reduction with the triazenido ligand set, and the monoalkyl complex (C(5)Me(5))(2)[(Me)NNN(Ad)-k(2)N(1.3)]U(CH(2)SiMe(3)), 13, can be isolated.

  DOI：

  10.1021/om9008179

文献信息

• Insertion of Carbodiimides and Organic Azides into Actinide−Carbon Bonds
  作者：William J. Evans、Justin R. Walensky、Joseph W. Ziller、Arnold L. Rheingold

  DOI：10.1021/om900135e

  日期：2009.6.22

  analogous product with iPrN═C═NiPr, but forms instead a complex formally derived from carbodiimide insertion into a “(C5Me5)2U(C6H4)” intermediate, (C5Me5)2U[(iPr)NC═N(iPr)(C6H4)-κN,κC], 4. Adamantyl azide, AdN3, inserts into the An−Me bonds in the (C5Me5)2AnMe2 complexes to make monomethyl actinide triazenido complexes that differ in the mode of triazenido coordination: (C5Me5)2ThMe[(Me)NN═N(Ad)-κ2N1,2],

  通过研究碳二亚胺（RN═C═NR）和有机叠氮化物（RN 3）与act系烷基，炔基和芳基配合物的插入化学，探索了对有机act系络合物中空间拥挤的操纵。我PrN═C═N我镨发生反应与（C 5我5）2 ANME 2，以产生同晶甲基脒基（C 5我5）2 ANME [（我PR）NC（ME）N（我PR）-κ 2 N，N']，An = Th，1 ; U，2，高产。的反应我PrN═C═N我Pr与（C 5 Me 5）2 U（C≡CPh）2形成相似的插入产物，（C 5 Me 5）2 U（C≡CPh）[（i Pr）NC（C≡CPh）N（i Pr ）-κ 2 N，N']，3。（C 5我5）2 ù（C 6 H ^ 5）2不会产生类似的产物与我PrN═C═N我PR，但形式而不是复杂的形式上从碳二亚胺衍生插入到一个“（C 5我5）2个U（C 6 H 4）”中间体，（C 5 Me 5）2 U [（i Pr）NC═N（i Pr）（C