[(1,7-Me₂TACD)Y(η³-C₃H₅)]₂ | 1415986-01-4

• 英文名称: [(1,7-Me₂TACD)Y(η³-C₃H₅)]₂
• 英文别名: [(1,7-dimethyl-1,4,7,10-tetraazacyclododecane)Y(η³-allyl)]₂ ；[{(1,7-dimethyl-1,4,7,10-tetra-azacyclododecane(-2H))Ln(h3-C3H5)}2]
• CAS: 1415986-01-4
• 化学式: C₂₆H₅₄N₈Y₂
• 分子量: 656.58
• InChiKey: PWGVYKQYEWDVPV-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：

  [(1,7-Me₂TACD)Y(η³-C₃H₅)]₂ 、 potassium allyl 以 四氢呋喃 为溶剂， 以88%的产率得到[(1,7-Me₂TACD)Y(η₃-C₃H₅)₂K(THF)]n
  参考文献：
  名称：

  Heterometallic Potassium Rare-Earth-Metal Allyl and Hydrido Complexes Stabilized by a Dianionic (NNNN)-Type Macrocyclic Ancillary Ligand

  摘要：

  The macrocyclic diamino diamine (1,7-Me(2)TACD)H-2 (1,7-Me(2)TACD = 1,7-dimethyl-1,4,7,10-tetraazacyclododecane, 1,7-Me-2[12]aneN(4)), reacted under propylene elimination with [Ln(eta(3)-C3H5)(3)(diox)] (Ln = Y, La) to give the mono(allyl) complexes [(1,7-Me(2)TACD)Ln(eta(3)-C3H5)](2) (Ln = Y (1a), La (1b)). A single-crystal X-ray diffraction study shows 1b to be a centrosymmetric dimer with lanthanum atoms bridged by one of the two amido nitrogen atoms. Complexes 1a,b were treated with 2 equiv of the potassium allyl KC3H5 to give the corresponding heterometallic allyl complexes [(1,7-Me(2)TACD)Ln(eta(3)-C3H5)(2)K(THF)](n) (Ln = Y (2a), La (2b)). A single-crystal X-ray diffraction study revealed that 2a,b are polymeric in the solid state with allyl ligands bridging the metal centers in addition to the presence of mu(2)-amido functions of the 1,7-Me(2)TACD ligand. Hydrogenolysis of the yttrium compound 2a with 1 bar of H-2 led to the formation of the heterometallic Y4K2 hydrido complex [(1,7-Me(2)TACD)(2)Y2H3K(THF)(2)](2) (3a), which can also be synthesized from a 1:1 mixture of 1a and KC3H5 with 1 bar of H-2. A single crystal X-ray diffraction study of 3a revealed a dimer of heterotrinuclear Y2K trihydride aggregate. Treatment of 2b with 1 bar of H-2 afforded the heptanuclear La3K4 heptahydrido complex [(1,7-Me(2)TACD)(3)La3H7K4(THF)(7)] (3b).

  DOI：

  10.1021/om300986w
• 作为产物：
  描述：

  [Y(η³-C₃H₅)₃(1,4-dioxane)] 、 1,7-dimethyl-1,4,7,10-tetra-azacyclododecane 以 四氢呋喃 为溶剂， 以63%的产率得到[(1,7-Me₂TACD)Y(η³-C₃H₅)]₂
  参考文献：
  名称：

  Heterometallic Potassium Rare-Earth-Metal Allyl and Hydrido Complexes Stabilized by a Dianionic (NNNN)-Type Macrocyclic Ancillary Ligand

  摘要：

  The macrocyclic diamino diamine (1,7-Me(2)TACD)H-2 (1,7-Me(2)TACD = 1,7-dimethyl-1,4,7,10-tetraazacyclododecane, 1,7-Me-2[12]aneN(4)), reacted under propylene elimination with [Ln(eta(3)-C3H5)(3)(diox)] (Ln = Y, La) to give the mono(allyl) complexes [(1,7-Me(2)TACD)Ln(eta(3)-C3H5)](2) (Ln = Y (1a), La (1b)). A single-crystal X-ray diffraction study shows 1b to be a centrosymmetric dimer with lanthanum atoms bridged by one of the two amido nitrogen atoms. Complexes 1a,b were treated with 2 equiv of the potassium allyl KC3H5 to give the corresponding heterometallic allyl complexes [(1,7-Me(2)TACD)Ln(eta(3)-C3H5)(2)K(THF)](n) (Ln = Y (2a), La (2b)). A single-crystal X-ray diffraction study revealed that 2a,b are polymeric in the solid state with allyl ligands bridging the metal centers in addition to the presence of mu(2)-amido functions of the 1,7-Me(2)TACD ligand. Hydrogenolysis of the yttrium compound 2a with 1 bar of H-2 led to the formation of the heterometallic Y4K2 hydrido complex [(1,7-Me(2)TACD)(2)Y2H3K(THF)(2)](2) (3a), which can also be synthesized from a 1:1 mixture of 1a and KC3H5 with 1 bar of H-2. A single crystal X-ray diffraction study of 3a revealed a dimer of heterotrinuclear Y2K trihydride aggregate. Treatment of 2b with 1 bar of H-2 afforded the heptanuclear La3K4 heptahydrido complex [(1,7-Me(2)TACD)(3)La3H7K4(THF)(7)] (3b).

  DOI：

  10.1021/om300986w

文献信息

• Dehydrogenation of AmineBorane Me₂NH⋅BH₃Catalyzed by a LanthanumHydride Complex
  作者：Peng Cui、Thomas P. Spaniol、Laurent Maron、Jun Okuda

  DOI：10.1002/chem.201301732

  日期：2013.9.27

  The rare‐earth‐metal hydride complexes [(1,7‐Me2TACD)LnH}4] (Ln=La 1 a, Y 1 b; (1,7‐Me2TACD)H2=1,7‐dimethyl‐1,4,7,10‐tetraazacyclododecane, 1,7‐Me2[12]aneN4) were synthesized by hydrogenolysis of [(1,7‐Me2TACD)Ln(η3‐C3H5)}2] with 1 bar H2. The tetrameric structures were confirmed by 1H NMR spectroscopy and single‐crystal X‐ray diffraction of compound 1 a. Both complexes catalyze the dehydrogenation

  稀土类金属氢化物络合物[（1,7-ME 2 TACD）LNH} 4 ]（LN =拉1，Y 1b中;（1,7-ME 2 TACD）H 2 = 1,7 -二甲基- 1,4,7,10-四，1,7--ME 2 [12] ANEN 4）通过氢解合成[（1,7-ME 2 TACD）LN（η 3 -C 3 H ^ 5）} 2 ]的压力为1 bar H 2。通过1 H NMR光谱和化合物1a的单晶X射线衍射确认了四聚体结构。两种复合催化仲胺的脱氢硼烷我2 NH ⋅ BH 3，得到环状二聚体（ME 2 NBH 2）2和（ME 2 N）2在温和条件下BH。尽管我的完全转化2 NH ⋅ BH 3在2小时内观察到与镧氢化物1，钇同源物1b中需要48小时以达到95％的转化。化合物的进一步的反应1中的与我2 NH ⋅ BH3以各种化学计量比得到一系列中间产物[（（1,7-Me 2 TACD）LaH} 4 ]（Me