[Th(pentamethylcyclopentadienyl)2Me((i-Pr)NC(Me)N(i-Pr)-κ2N,N') | 1160174-43-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [Th(pentamethylcyclopentadienyl)2Me((i-Pr)NC(Me)N(i-Pr)-κ2N,N')
• 英文别名: (pentamethylcyclopentadienyl)2[(i-Pr)NC(Me)N(i-Pr)-κ2N,N']ThMe；(C5Me5)2[(i)PrNC(Me)N(i)Pr]ThMe；carbanide;(C-methyl-N-propan-2-ylcarbonimidoyl)-propan-2-ylazanide;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;thorium(4+)
• CAS: 1160174-43-5
• 化学式: C₂₉H₅₀N₂Th
• 分子量: 658.767
• InChiKey: BQMBYKDTQSDGFV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.94
• 重原子数：
  32
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  13.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [Th(pentamethylcyclopentadienyl)2Me((i-Pr)NC(Me)N(i-Pr)-κ2N,N') 、 三苯基硼烷 在 KC₈ 作用下， 以 四氢呋喃 为溶剂， 以86%的产率得到(C5Me5)2[(i)PrNC(Me)N(i)Pr]Th
  参考文献：
  名称：

  Importance of Energy Level Matching for Bonding in Th³⁺-Am³⁺ Actinide Metallocene Amidinates, (C₅Me₅)₂[ⁱPrNC(Me)NⁱPr]An

  摘要：

  The synthesis of a rare trivalent Th3+ complex, (C5Me5)(2)[(PrNC)-Pr-i(Me)(NPr)-Pr-i]Th, initiated a density functional theory analysis on the electronic and molecular structures of trivalent actinide complexes of this type for An = Th, Pa, U, Np, Pu, and Am. While the 6d orbital is found to accommodate the unpaired spin in the Th3+ species, the next member of the series, Pa, is characterized by an f(2) ground state, and later actinides successively fill the 5f shell. In this report, we principally examine the evolution of the bonding as one advances along the actinide row. We find that the early actinides (Pa-Np) are characterized by localized f orbitals and essentially ionic bonding, whereas the f orbitals in the later members of the series (Pu, Am) exhibit significant interaction and spin delocalization into the carbon- and nitrogen-based ligand orbitals. This is perhaps counter-intuitive since the f orbital radius and hence metal-ligand overlap decreases with increasing Z, but this trend is counter-acted by the fact that the actinide contraction also leads to a stabilization of the f orbital manifold that leads to a near degeneracy between the An 5f and cyclopentadienyl pi-orbitals for Pu and Am, causing a significant orbital interaction.

  DOI：

  10.1021/ic1013285
• 作为产物：
  描述：

  dimethylbis(η5-pentamethylcyclopentadienyl)thorium 、 N,N'-二异丙基碳二亚胺 以 甲苯 为溶剂， 以97%的产率得到[Th(pentamethylcyclopentadienyl)2Me((i-Pr)NC(Me)N(i-Pr)-κ2N,N')
  参考文献：
  名称：

  将碳二亚胺和有机叠氮化物插入到Act系碳键中

  摘要：

  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

  DOI：

  10.1021/om900135e

文献信息

• Reactivity of Methyl Groups in Actinide Metallocene Amidinate and Triazenido Complexes with Silver and Copper Salts
  作者：William J. Evans、Justin R. Walensky、Joseph W. Ziller

  DOI：10.1021/om9008179

  日期：2010.1.11

  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.