[Rh(1,5-cyclooctadiene)(bis(methimazolyl)methane)]BF4 | 887148-21-2

• 英文名称: [Rh(1,5-cyclooctadiene)(bis(methimazolyl)methane)]BF4
• CAS: 887148-21-2
• 化学式: BF₄*C₁₇H₂₄N₄RhS₂
• 分子量: 538.246
• InChiKey: CZVAKHJGZANNFX-ONEVTFJLSA-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：

  二氯甲烷 、 [Rh(1,5-cyclooctadiene)(bis(methimazolyl)methane)]BF4 、 2,6-二甲基苯基异腈 以 二氯甲烷 为溶剂， 生成 [Rh(CNC6H3Me2-2,6)2(bis(methimazolyl)methane)]BF4*0.5CH2Cl2
  参考文献：
  名称：

  A Less Carbocentric View of Agostic Interactions:  The Complexes [Rh(η⁴-cod){H₂A(mt)₂}] (A = B, C⁺; mt = Methimazolyl)

  摘要：

  The reaction of [Rh-2(mu-Cl)(2)(cod)(2)] (cod = 1,5-cyclooctadiene) with Na[H2B(mt)(2)] (mt = methimazolyl) provides the complex [Rh(cod){H2B(mt)(2)}] (1), which in turn reacts with CO or CNC6H3Me2-2,6 to provide the derivatives [RhL2{H2B(mt)(2)}] (L = CO (2), CNC6H3Me2-2,6 (3)). In a similar manner [Rh-2-(mu-Cl)(2)(cod)(2)] reacts with H2C(Mt)(2) to provide the cationic complex [Rh(cod){H2C(mt)(2)}](+) (4(+)), which was isolated after counteranion metathesis as either 4-BF4 or 4 center dot PF6. Carbonylation of 4-PF6 provides [Rh(CO)(2){H2C)(mt)(2)}]PF6 (5 center dot PF6); however, the reaction is reversible in the presence of cod, regenerating 4-PF6 under reduced pressure. The reactions of 4-PF6 with CNC6H3Me2-2,6 or CNCMe3 provide respectively the salts [Rh(CNC6H3Me2-2,6)(2){H2C(mt)(2)}]PF6 (6-PF6) and [Rh(CNCMe3)(4)]PF6. The crystal structures of 1, 4-BF4, 4-PF6, and 6-BF4 reveal long B-H...Rh or C-H...Rh interactions; however, such an interaction is effectively absent for 5-PF6-CHCl3, while solution spectroscopy (H-1 NMR and IR) indicates that none of these interactions persist in solution. The complexes 1 and 4(+) represent the first structurally characterized isoelectronic pair involving, albeit weak, three-center-two-electron B-H-metal or C-H-metal interactions.

  DOI：

  10.1021/om050942i
• 作为产物：
  描述：

  bis(1-methyl-imidazole-2-thione)methane 、 氟硼酸钠 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 以 甲醇 为溶剂， 生成 [Rh(1,5-cyclooctadiene)(bis(methimazolyl)methane)]BF4
  参考文献：
  名称：

  A Less Carbocentric View of Agostic Interactions:  The Complexes [Rh(η⁴-cod){H₂A(mt)₂}] (A = B, C⁺; mt = Methimazolyl)

  摘要：

  The reaction of [Rh-2(mu-Cl)(2)(cod)(2)] (cod = 1,5-cyclooctadiene) with Na[H2B(mt)(2)] (mt = methimazolyl) provides the complex [Rh(cod){H2B(mt)(2)}] (1), which in turn reacts with CO or CNC6H3Me2-2,6 to provide the derivatives [RhL2{H2B(mt)(2)}] (L = CO (2), CNC6H3Me2-2,6 (3)). In a similar manner [Rh-2-(mu-Cl)(2)(cod)(2)] reacts with H2C(Mt)(2) to provide the cationic complex [Rh(cod){H2C(mt)(2)}](+) (4(+)), which was isolated after counteranion metathesis as either 4-BF4 or 4 center dot PF6. Carbonylation of 4-PF6 provides [Rh(CO)(2){H2C)(mt)(2)}]PF6 (5 center dot PF6); however, the reaction is reversible in the presence of cod, regenerating 4-PF6 under reduced pressure. The reactions of 4-PF6 with CNC6H3Me2-2,6 or CNCMe3 provide respectively the salts [Rh(CNC6H3Me2-2,6)(2){H2C(mt)(2)}]PF6 (6-PF6) and [Rh(CNCMe3)(4)]PF6. The crystal structures of 1, 4-BF4, 4-PF6, and 6-BF4 reveal long B-H...Rh or C-H...Rh interactions; however, such an interaction is effectively absent for 5-PF6-CHCl3, while solution spectroscopy (H-1 NMR and IR) indicates that none of these interactions persist in solution. The complexes 1 and 4(+) represent the first structurally characterized isoelectronic pair involving, albeit weak, three-center-two-electron B-H-metal or C-H-metal interactions.

  DOI：

  10.1021/om050942i