[η⁵-1,2,4-(Me3C)3C5H2]2Th=N(p-tolyl) | 1323150-26-0

• 英文名称: [η⁵-1,2,4-(Me3C)3C5H2]2Th=N(p-tolyl)
• 英文别名: [η5-1,2,4-(Me3C)3C5H2]2Th=N(p-tolyl)；[η5-1,2,4-(Me3C)3C5H2]2Th=N-p-tolyl
• CAS: 1323150-26-0
• 化学式: C₄₁H₆₅NTh
• 分子量: 804.012
• InChiKey: RTGREUJREQKGJK-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：

  [η⁵-1,2,4-(Me3C)3C5H2]2Th=N(p-tolyl) 在 selenium 作用下， 以 甲苯 为溶剂， 以80%的产率得到
  参考文献：
  名称：

  Small Molecule Activation Mediated by a Thorium Terminal Imido Metallocene

  摘要：

  The base-free thorium terminal imido [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th=N(p-tolyl) (1) activates a variety of small molecules such as pyridine derivatives, amines, boranes, chlorosilane, elemental selenium, and alpha,beta-unsaturated esters. Reaction of 1 with pyridine, pyridine N-oxide, 2-methylpyridine N-oxide, p-toluidine, Ph2NH, 9-borabicyclo[3.3.1]nonane (9-BBN), PhSiH2Cl, elemental selenium, PhSeSePh, and methyl methacrylate (MMA) formed the amido pyridyl complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,N-C5H4N) (2), [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,O-C5H4NO) (3), and [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,O-2-MeC5H3NO) (4), diamide complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(2) (5) and [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(NPh2) (6), amido hydrido complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(H)[N(p-tolyl)B(C8H14)] (7), amido chloride complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(Cl)[N(p-tolyl)SiH2Ph] (8), amido selenido complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th[N(p-tolyl)SeSe] (9) and {[eta(5)-1,2,4-(Me3C)(3)C5H2]Th(SePh)}(2)[mu-N(p-tolyl)](2) (10), and amido enolyl complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th[N(p-tolyl)CH2C(Me)=C(OMe)O] (11). The new complexes 2-3 and 6-11 were characterized by various spectroscopic techniques including single crystal X-ray diffraction. Furthermore, density functional theory (DFT) studies complement the experimental investigations.

  DOI：

  10.1021/acs.organomet.5b00454
• 作为产物：
  描述：

  [η⁵-1,2,4-(Me₃C)₃C₅H₂]2Th(NH-p-tolyl)₂ 140.0 ℃ 、1.33 Pa 条件下， 生成 [η⁵-1,2,4-(Me3C)3C5H2]2Th=N(p-tolyl)
  参考文献：
  名称：

  Small Molecule Activation Mediated by a Thorium Terminal Imido Metallocene

  摘要：

  The base-free thorium terminal imido [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th=N(p-tolyl) (1) activates a variety of small molecules such as pyridine derivatives, amines, boranes, chlorosilane, elemental selenium, and alpha,beta-unsaturated esters. Reaction of 1 with pyridine, pyridine N-oxide, 2-methylpyridine N-oxide, p-toluidine, Ph2NH, 9-borabicyclo[3.3.1]nonane (9-BBN), PhSiH2Cl, elemental selenium, PhSeSePh, and methyl methacrylate (MMA) formed the amido pyridyl complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,N-C5H4N) (2), [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,O-C5H4NO) (3), and [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(eta(2)-C,O-2-MeC5H3NO) (4), diamide complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(2) (5) and [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(NH-p-tolyl)(NPh2) (6), amido hydrido complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(H)[N(p-tolyl)B(C8H14)] (7), amido chloride complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(Cl)[N(p-tolyl)SiH2Ph] (8), amido selenido complexes [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th[N(p-tolyl)SeSe] (9) and {[eta(5)-1,2,4-(Me3C)(3)C5H2]Th(SePh)}(2)[mu-N(p-tolyl)](2) (10), and amido enolyl complex [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th[N(p-tolyl)CH2C(Me)=C(OMe)O] (11). The new complexes 2-3 and 6-11 were characterized by various spectroscopic techniques including single crystal X-ray diffraction. Furthermore, density functional theory (DFT) studies complement the experimental investigations.

  DOI：

  10.1021/acs.organomet.5b00454

文献信息

• Experimental and Computational Studies on the Reactivity of a Terminal Thorium Imidometallocene towards Organic Azides and Diazoalkanes
  作者：Wenshan Ren、Enwei Zhou、Bo Fang、Guohua Hou、Guofu Zi、De-Cai Fang、Marc D. Walter

  DOI：10.1002/anie.201406191

  日期：2014.10.13

  The reaction of the base‐free terminal thorium imido complex [η5‐1,2,4‐(Me3C)3C5H2}2ThN(p‐tolyl)] (1) with p‐azidotoluene yielded irreversibly the tetraazametallacyclopentene [η5‐1,2,4‐(Me3C)3C5H2}2ThN(p‐tolyl)NNN(p‐tolyl)}] (2), whereas the bridging imido complex [[η5‐1,2,4‐(Me3C)3C5H2]Th(N3)2}2μ‐N(p‐tolyl)}2][(n‐C4H9)4N]2 (3) was isolated from the reaction of 1 with [(n‐C4H9)4N]N3. Unexpectedly

  游离碱末端钍酰亚胺络合物的反应[η 5 -1,2,4-（ME 3 C）3 c ^ 5 ħ 2 } 2 ThN（对甲苯基）]（1）与p -azidotoluene产生不可逆的tetraazametallacyclopentene [η 5 -1,2,4-（ME 3 C）3 c ^ 5 ħ 2 } 2的Th N（p -甲苯基）NN  N（p -甲苯基）}]（2）的，而桥接亚氨基配合物[[η 5 -1,2,4-（ME 3 C）3 C ^5 ħ 2 ]的Th（N 3）2 } 2 μ-N（p -甲苯基）} 2 ] [（Ñ -C 4 ħ 9）4 N] 2（3）从反应中分离1与[（n C 4 H 9）4 N] N 3。出乎意料的是，在所述治疗的1用9- diazofluorene，N-N键裂解，N原子被转移，并且η 2 -diazenido iminato复杂[η 5 -1,2,4-（ME
• Thorium Oxo and Sulfido Metallocenes: Synthesis, Structure, Reactivity, and Computational Studies
  作者：Wenshan Ren、Guofu Zi、De-Cai Fang、Marc D. Walter

  DOI：10.1021/ja205280k

  日期：2011.8.24

  4-(Me(3)C)(3)C(5)H(2)](2)Th═N(p-tolyl) (4), which is a useful precursor for the preparation of oxo and sulfido thorium metallocenes [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)Th═E (E = O (5) and S (15)) by cycloaddition-elimination reaction with Ph(2)C═E (E = O, S) or CS(2). The oxo metallocene 5 acts as a nucleophile toward alkylsilyl halides, while sulfido metallocene 15 does not. The oxo metallocene 5 and sulfido

  已经全面研究了氧化钍和硫化金属茂的合成、结构和反应性。加热二甲基茂金属 [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)ThMe(2) (2) 的等摩尔混合物和双酰胺茂金属 [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)Th(NH-p-tolyl)(2 ) (3) 在回流甲苯中产生无碱的亚氨基钍茂金属，[η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2 )Th=N(p-tolyl) (4)，它是制备氧代和硫化钍金属茂的有用前体 [η(5)-1,2,4-(Me(3)C)(3)C (5)H(2)](2)Th=E (E = O (5) 和 S (15)) 通过与 Ph(2)C=E (E = O, S) 或 CS( 2）。氧代金属茂 5 充当对烷基甲硅烷基卤化物的亲核试剂，而硫代金属茂 15 则不然。羰基茂金属 5 和硫化茂金属 15
• A Base-Free Terminal Actinide Phosphinidene Metallocene: Synthesis, Structure, Reactivity, and Computational Studies
  作者：Congcong Zhang、Guohua Hou、Guofu Zi、Wanjian Ding、Marc D. Walter

  DOI：10.1021/jacs.8b09746

  日期：2018.10.31

  The synthesis, structure, and reactivity of a base-free terminal actinide phosphinidene metallocene have been comprehensively studied. The salt metathesis reaction of the thorium methyl iodide complex Cp‴2Th(I)Me (2; Cp‴ = η5-1,2,4-(Me3C)3C5H2) with Mes*PHK (Mes* = 2,4,6-(Me3C)3C6H2) in THF furnishes the first stable base-free terminal phosphinidene actinide metallocene, Cp‴2Th═PMes* (3). Density functional

  已经全面研究了无碱末端锕系膦亚茂金属茂的合成、结构和反应性。甲基碘化钍配合物 Cp‴2Th(I)Me (2; Cp‴ = η5-1,2,4-(Me3C)3C5H2) 与 Mes*PHK (Mes* = 2,4,6-) 的盐复分解反应(Me3C)3C6H2) 在 THF 中提供了第一个稳定的无碱末端膦亚锕系茂金属，Cp‴2Th=PMes* (3)。密度泛函理论 (DFT) 表明，Cp‴2Th2+ 和 [PMes*]2- 片段之间的键比相关的亚钍复合物中的键更共价。虽然膦化物配合物 3 对炔烃没有反应性，但它​​与各种杂不饱和分子如 CS2、异硫氰酸酯、腈、异腈和有机叠氮化物反应，形成二硫代碳化物、酰亚胺配合物、金属氮丙啶和叠氮化合物。
• Si–H addition followed by C–H bond activation induced by a terminal thorium imido metallocene: a combined experimental and computational study
  作者：Wenshan Ren、Enwei Zhou、Bo Fang、Guofu Zi、De-Cai Fang、Marc D. Walter

  DOI：10.1039/c4sc00576g

  日期：——

  unsaturated molecules into the Th–H bond, whereas complex 3 reversibly activates an intramolecular aromatic C–H bond to yield [η5-1,2,4-(Me3C)3C5H2]2Th[η2-N,C-N(p-MeC6H3)(SiHPh2)}] (4) and H2. The experimental results have been complemented by density functional theory (DFT) studies and provide a detailed understanding of the observed reactivity. In addition, a comparison between Th and early transition

  全面研究了末端act系亚氨基配合物的Si-H键加成。游离碱，钍酰亚胺[η 5 -1,2,4-（ME 3 C）3 c ^ 5 ħ 2 ] 2的Th N（p -甲苯基）（1）激活PhSiH SiH键3或PH 2的SiH 2，得到钍酰氨基氢基的金属茂[η 5 -1,2,4-（ME 3 C）3 c ^ 5 ħ 2 ] 2的Th（H）[N（p -甲苯基）的SiH 2 PH]（2）和[ η5 -1,2,4-（Me 3 C） 3 C 5 H 2 ] 2 Th（H）[N（对甲苯基）SiHPh 2 ]（ 3）。复杂2容易插入的不饱和分子进入的Th-H键，而复杂的3可逆激活的分子内芳香C-H键以产率[η 5 -1,2,4-（ME 3 C） 3 c ^ 5 ħ 2 ] 2的Th [η 2 - ñ， ç - N（ p -MeC 6 ħ 3）（SiHPh 2）}]（4）和H 2。实验结果得到密度泛函理论（DFT）
• Synthesis, Structure, and Reactivity of a Thorium Metallocene Containing a 2,2′-Bipyridyl Ligand
  作者：Wenshan Ren、Guofu Zi、Marc D. Walter

  DOI：10.1021/om201015f

  日期：2012.1.23

  The reduction of [eta(5)-1,2,4-(Me3C)(3)C5H2](2)ThCl2 (1) with potassium graphite in the presence of 2,2'-bipyridine gives the purple thorium bipy metallocene [eta(5)-1,2,4-(Me3C)(3)C5H2](2)Th(bipy) (2) in good yield. Complex 2 has been characterized by various spectroscopic techniques, elemental analysis, and single-crystal X-ray diffraction. Complex 2 is a good synthon for low-valent thorium, as shown by the reactivity with silver halides, trityl chloride, pyridine-N-oxide, RN3, 9-diazofluorene, and diphenyl diselenide, yielding the halide metallocenes [eta(3)-1,2,4-(Me3C)(3)C5H2](2)ThX2 (X = Cl (1), F (3), Br (4)), oxo metallocene [eta(3)-1,2,4-(Me3C)(3)C5H2](2)ThO(py) (5), imido metallocenes (Me3C)(3)C5H2](2)Th=NR (R = p-tolyl (6), Ph3C (7), Me3Si (8), (9-C13H8)=N (9)), and selenido complex [eta(3-)1.2.4-(Me3C)(3)C5H2]Th(SePh)(3)(bipy) (10a), in quantitative conversions.