trans-[((Ph2P(o-C6H4)CH2NHCMe2)2)RuHCl] | 823788-59-6

• 英文名称: trans-[((Ph2P(o-C6H4)CH2NHCMe2)2)RuHCl]
• 英文别名: RuHCl(1,6-bis((2-diphenylphosphino)benzo)-3,3,4,4-tetramethyl-2,5-diaza-1,5-hexane)
• CAS: 823788-59-6；824410-42-6
• 化学式: C₄₄H₄₇ClN₂P₂Ru
• 分子量: 802.341
• InChiKey: IYBZOYUIUTWMAX-UHFFFAOYSA-M

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：

  trans-[((Ph2P(o-C6H4)CH2NHCMe2)2)RuHCl] 在 KO(t)Bu 作用下， 以 甲苯 为溶剂， 以79%的产率得到[(Ph2P(o-C6H4)CH2NCMe2CMe2NHCH2(o-C6H4)PPh2)RuH]
  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
• 作为产物：
  描述：

  RuHCl(1,6-bis((2-diphenylphosphino)benzo)-3,3,4,4-tetramethyl-2,5-diaza-1,5-hexane) 以 二氯甲烷 为溶剂， 生成 trans-[((Ph2P(o-C6H4)CH2NHCMe2)2)RuHCl]
  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

文献信息

• Hydrogenation of Benzonitrile to Benzylamine Catalyzed by Ruthenium Hydride Complexes with P−NH−NH−P Tetradentate Ligands:  Evidence for a Hydridic−Protonic Outer Sphere Mechanism
  作者：Tianshu Li、Ines Bergner、F. Nipa Haque、Marco Zimmer-De Iuliis、Datong Song、Robert H. Morris

  DOI：10.1021/om700783e

  日期：2007.11.1

  theoretical (DFT) evidence is presented for a new mechanism for nitrile hydrogenation:  the successive hydrogenation of the CN triple bond and then the CN double bond of the intermediate imine by H+/H- transfer from a trans dihydride active catalyst. The amido complex RuHtmeP2N(NH)} (4) has similar activity to 3/base for the base-free hydrogenation of benzonitrile and is moderately active for the catalytic

  RuHCl（PPh 3）3与四齿配体[PPh 2（（邻-C 6 H 4）CH 2 NHCH 2-）] 2 ethP 2（NH） 2 }在四氢呋喃中生成新的复合反式RuHCl ethP 2（NH） 2 }（ 1），为两种异构体的混合物。当用KO t Bu / KH活化时，RuHCl ethP 2（NH） 2 }（ 1）络合物是一种非常活泼的催化剂，用于将甲苯中的苯甲腈氢化为苄胺，比已知的催化剂Ru（H 2） 2 H具有更高的活性2（PCy 3） 2（ 2）。1和2的混合物并且碱还导致苄腈有效地转化为苄胺。络合物RuHCl tmeP 2（NH）2 }（3），其中tmeP 2（NH）2为[PPh 2（（邻位-C 6 H 4）CH 2 NHCMe 2-）] 2是用于该反应的活性较低的催化剂。这些催化剂体系对空气敏感，对湿气极为敏感。实验和理论（DFT）的证据提出了一种用于对腈加氢的新机制：
• An acidity scale of phosphonium tetraphenylborate salts and ruthenium dihydrogen complexes in dichloromethane
  作者：Tianshu Li、Alan J Lough、Cristiano Zuccaccia、Alceo Macchioni、Robert H Morris

  DOI：10.1139/v05-236

  日期：2006.2.1

  Equilibrium constants (K^DM) for reactions between acids and bases of the title compounds in CD₂Cl₂ (DM) have been determined by ³¹P and ¹H NMR spectroscopy at room temperature. [HPCy₃]BPh₄ and [HPCy₃]BF₄, with pK^DM assigned by literature convention to 9.7, have been used as the anchor compounds for the pK^DM determinations. A continuous scale of pK^DM values covering the range 9.7 to 5.7 is created with the acidic compounds [HPR₃]BPh₄. Those acids with pK^DM greater than 6 are stable, while those with more acidic cations HPR₃⁺ protonate BPh₄^– to produce R₃PBPh₃ and benzene. The literature pK^THF values reported for [HPBu₂Ph]BPh₄, [HPMePh₂]BPh₄, and [HPEtPh₂]BPh₄ are questionable because of this protonation reaction. NOE and PGSE ¹H NMR techniques are used to show that [HPCy₂Ph]BPh₄ in DM exists as ion pairs and higher aggregates up to quadrupoles at the concentrations used in the acid–base studies. The new dihydrogen complexes [Ru(H₂)Cl(PPh₃)₂(dach)]BF₄ (dach = (1R,2R)-(–)-diaminocyclohexane) and [Ru(H₂)CltmeP₂(NH)₂}]BF₄ (tmeP₂(NH)₂ = PPh₂C₆H₄CH₂NHCMe₂CMe₂NHCH₂C₆H₄PPh₂) were prepared by reaction of RuHCl(PPh₃)₂(dach) and RuHCltmeP₂(NH)₂} with HBF₄. Their crystal structures are reported, and the pK^DM values of their BPh₄^– salts were determined to be 8.6 and 6.9, respectively.Key words: acidity, dihydrogen complex, hydride, phosphonium, dichloromethane.

  在室温下，通过 31P 和 1H NMR 光谱测定了标题化合物在 CD2Cl2（DM）中酸碱反应的平衡常数（KDM）。根据文献惯例，pKDM 值为 9.7 的 [HPCy3]BPh4 和 [HPCy3]BF4 被用作测定 pKDM 值的锚化合物。酸性化合物 [HPR3]BPh4 的 pKDM 值从 9.7 到 5.7 不等。pKDM 值大于 6 的酸性化合物是稳定的，而那些酸性阳离子 HPR3+ 会质子化 BPh4，生成 R3PBPh3 和苯。由于这种质子化反应，文献中报道的 [HPBu2Ph]BPh4、[HPMePh2]BPh4 和 [HPEtPh2]BPh4 的 pKTHF 值值得怀疑。NOE 和 PGSE 1H NMR 技术表明，在酸碱研究中使用的浓度下，DM 中的[HPCy2Ph]BPh4 以离子对和更高聚集体的形式存在，最高可达四极。新的二氢配合物[Ru(H2)Cl(PPh3)2(dach)]BF4（dach = (1R、2R)-()-diaminocyclohexane) 和 [Ru(H2)CltmeP2(NH)2}]BF4 (tmeP2(NH)2 = PPh2C6H4CH2NHCMe2CMe2NHCH2C6H4PPh2) 是通过 RuHCl(PPh3)2(dach) 和 RuHCltmeP2(NH)2} 与 HBF4 反应制备的。报告了它们的晶体结构，并测定了它们的 BPh4 盐的 pKDM 值分别为 8.6 和 6.9。