| 1594927-65-7

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• CAS: 1594927-65-7
• 化学式: C₈H₂₂Ge₂
• 分子量: 263.443
• InChiKey: ORJZQNBXRMVIGZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.68
• 重原子数：
  10.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  tert-butylgermane 在 [(PhB(CH₂PPh₂)₃)₃]RuH[η³-H₂SiMePh] 作用下， 以 氘代苯 为溶剂， 反应 24.0h， 以85%的产率得到
  参考文献：
  名称：

  Interconversion of η³-H₂SiRR′ σ-Complexes and 16-Electron Silylene Complexes via Reversible H–H or C–H Elimination

  摘要：

  Solid samples of eta(3)-silane complexes [PhBP3Ph](-) RuH(eta(3)-H2SiRR') (R,R' = Et-2, 1a; PhMe, 1b; Pb-2, 1c, MeMes, 1d) decompose when exposed to dynamic vacuum. Gas-phase H-2/D-2 exchange between isolated, solid samples of 1c-d(3) and 1c indicate that a reversible elimination of H-2 is the first step in the irreversible decomposition. An efficient solution-phase trap for hydrogen, the 16-electron ruthenium benzyl complex [PhBPPb3]Ru[eta(3)-CH2(3,5-Me2C6H3)] (3) reacts quantitatively with H2 in benzene via elimination of mesitylene to form the eta(5)-cyclohexadienyl complex [PhBP3Ph]Ru(eta(5)-C6H7) (4). This H2 trapping reaction was utilized to drive forward and quantify the elimination of H-2 from 1b,d in solution, which resulted in the decomposition of 1b,d to form 4 and several organosilicon products that could not be identified. Reaction of {[PhBP3Ph]Ru(mu-Cl)}(2) (2) with (THF)(2)Li(SiHMes(2)) forms a new eta(3)-H2Si species [PhBP3Ph]Ru[CH2(2-(eta(3)-H(2)SiMes)-3,5-Me2C6H2)] (5) which reacts with H-2 to form the eta(3)-H(2)SiMes(2) complex [PhBP3Ph]RuH(eta(3)-H(2)SiMes(2)) (1e). Complex 1e was identified by NMR spectroscopy prior to its decomposition by elimination of Mes(2)SiH(2) to form 4. DFT calculations indicate that an isomer of 5, the 16-electron silylene complex [PhBP3Ph]Ru(mu-H)(= SiMes(2)), is only 2 kcal/mol higher in energy than 5. Treatment of 5 with XylNC (Xyl = 2,6-dimethylphenyl) resulted in trapping of [PhBP3Ph]Ru(mu-H)(=SiMes(2)) to form the 18-electron silylene complex [PhBP3Ph]Ru(CNXyl)(mu-H)(=SiMes(2)) (6). A closely related germylene complex [PhBP3Ph]Ru[CN(2,6-diphenyl-4-MeC6H2)](H)(=(GeHBu)-Bu-t) (8) was prepared from reaction of (BuGeH3)-Bu-t with the benzyl complex [PhBP3Ph]Ru[CN(2,6-diphenyl-4-MeC6H2)][eta(1)-CH2(3,5-Me2C6H3)] (7). Single crystal XRD analysis indicated that unlike for 6, the hydride ligand in 8 is a terminal hydride that does not engage in 3c-2e Ru-H -> Ge bonding. Complex 1b is an effective precatalyst for the catalytic Ge-H dehydrocoupling of (BuGeH3)-Bu-t to form ((BuGeH2)-Bu-t)(2) (85% yield) and H-2.

  DOI：

  10.1021/ja501803w