1,6-bis((2-diphenylphosphino)benzo)-3,3,4,4-tetramethyl-2,5-diaza-1,5-hexadiene | 823788-57-4

• 英文名称: 1,6-bis((2-diphenylphosphino)benzo)-3,3,4,4-tetramethyl-2,5-diaza-1,5-hexadiene
• 英文别名: 1-(2-diphenylphosphanylphenyl)-N-[3-[(2-diphenylphosphanylphenyl)methylideneamino]-2,3-dimethylbutan-2-yl]methanimine
• CAS: 823788-57-4
• 化学式: C₄₄H₄₂N₂P₂
• 分子量: 660.778
• InChiKey: WHDONXNOSCTYLC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.3
• 重原子数：
  48
• 可旋转键数：
  11
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  hydridochlorotris(triphenylphosphine)ruthenium(II) 、 1,6-bis((2-diphenylphosphino)benzo)-3,3,4,4-tetramethyl-2,5-diaza-1,5-hexadiene 以 四氢呋喃 为溶剂， 以75%的产率得到RuHCl(1,6-bis((2-diphenylphosphino)benzo)-3,3,4,4-tetramethyl-2,5-diaza-1,5-hexadiene)
  参考文献：
  名称：

  Dihydridoamine and Hydridoamido Complexes of Ruthenium(II) with a Tetradentate P−N−N−P Donor Ligand

  摘要：

  The new diphosphinediimine ligand PPh2C6H4CH=NCMe2CMe2N=CHC6H4PPh2 {tmeP(2)N(2)} is prepared by reacting NH2CMe2CMe2NH2 with 2 equiv of PPh2(C6H4-2-CHO). The diamine derivative PPh(2)C(6)H(4)CH(2)NHCMe(2)cMe(2)NHCH(2)C(6)HIPPh(2) {tmeP(2)(NH)(2)} is prepared by reducing tmeP(2)N(2) with LiAlH4. The reaction of RuHCl(PPh3)(3) with tmeP(2)N(2) in THF produces the complex trans-RuHCl{tmeP(2)N(2)}, while a similar reaction of RuHCl(PPh3)(3) with tmeP(2)(NH)(2) gives the complex trans-RuHCl{tmeP(2)(NH)(2)}, as a mixture of two isomers. The isomer with two N-H bonds syn to the Ru-H bond is converted on heating to an isomer thought to have one N-H syn to the Ru-H. The reaction of the two isomers with (KOBu)-Bu-t under Ar in toluene produces the novel hydridoamido complex RuH{tmeP(2)NNH}, where the ligand is deprotonated at one nitrogen. Reaction of this amido complex with H-2 gives exclusively the dihydridoamine complex transRu(H)(2){tmeP(2)(NH)(2)}. The complexes have been characterized by X-ray crystallography, NMR, IR, elemental analysis, and a deuterium exchange study. Complex RuH{tmeP(2)NNH}, or a combination of RuHCl{tmeP(2)(NH)(2)} and (KOBu)-Bu-t, slowly catalyzes the hydrogenation of acetophenone (6 atm H-2, 20 degreesC, benzene or 2-propanol). The catalytic cycle is thought to be similar to that for the ketone hydrogenation precatalyst trans-RuHCl{(S,S)-cyP(2)(NH)(2))}. However in the present work both of the proposed catalysts transRuH(2){tmeP(2)(NH)(2)} and RuH{tmeP(2)NNH} have been completely characterized. The tmeP2(NH)2 system, with hindering methyl groups, is less active than the cyP(2)(NH)(2) system with a trans-1,2-substituted cyclohexyl backbone. The variable configuration of the amine nitrogens that is observed for the tmeP(2)(NH)(2) complexes might also occur in the cyP(2)(NH)(2) systems and could explain the inconsistent selectivity of such catalysts. The diimine complex RuHCl{tmeP(2)N(2)} reacts with (KOBu)-Bu-t under H-2 to produce the dihydridodiamine complex trans-Ru(H)(2){tmeP(2)(NH)(2)}, the catalyst for the hydrogenation of acetophenone.

  DOI：

  10.1021/om049565k