RuCl2(NBD)2(py)2 | 59992-79-9

• 英文名称: RuCl2(NBD)2(py)2
• 英文别名: trans,cis-[RuCl₂(nbd)(py)₂]；trans,cis-[RuCl₂(2,5-norbornadiene)(pyridine)₂]；RuCl2(norbornadiene)(pyridine)；[η4-norbornadiene)Rh(pyridine)2Cl2]；RuCl2(norbornadiene)(pyridine)2；[RuCl2(py)2(nbd)]
• CAS: 59992-79-9
• 化学式: C₁₇H₁₈Cl₂N₂Ru
• 分子量: 422.319
• InChiKey: JLZNUJPUUUAOKZ-LACOCIHISA-L

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：

  RuCl2(NBD)2(py)2 、 1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene 以 四氢呋喃 为溶剂， 生成 RuCl2(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)(pyridine)2
  参考文献：
  名称：

  Ruthenium Complexes of the 1,4-Bis(diphenylphosphino)-1,3-butadiene-Bridged Diphosphine 1,2,3,4-Me₄-NUPHOS:  Solvent-Dependent Interconversion of Four- and Six-Electron Donor Coordination and Transfer Hydrogenation Activity

  摘要：

  In chloroform, [RuCl2(nbd)(py)(2)] (1) (nbd = norbornadiene; py = pyridine) reacts with 1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene (1,2,3,4-Me-4-NUPHOS) to give the dimer [Ru2Cl3(eta(4)-1,2,3,4-Me-4-NUPHOS)(2)]Cl (2a), whereas, in THF [RuCl2(1,2,3,4-Me-4-NUPHOS)(PY)(2)] (3) is isolated as the sole product of reaction. Compound 2 exists as a 4:1 mixture of two noninterconverting isomers, the major with C, symmetry and the minor with either C, or C-2 symmetry. A single-crystal X-ray analysis of [Ru2Cl3 (eta(4)-1,2,3,4-Me-4-NUPHOS)(2)] [SbF6] (2b), the hexafluoroantimonate salt of 2a, revealed that the diphosphine coordinates in an unusual manner, as a eta(4)-six-electron donor, bonded through both P atoms and one of the double bonds of the butadiene tether. Compounds 2a and 3 react with 1,2-ethylenediamine (en) in THF to afford [RuCl2(1,2,3,4-Me-4-NUPHOS)(en)] (4), which rapidly dissociates a chloride ligand in chloroform to give [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)] [Cl] (5a). Complexes 4 and 5a cleanly and quantitatively interconvert in a solvent-dependent equilibrium, and in THF 5a readily adds chloride to displace the eta(2)-interaction and re-form 4. A single-crystal X-ray structure determination of [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)][ClO4] (5b) confirmed that the diphosphine coordinates in an eta(4)-manner as a facial six-electron donor with the eta(2)-coordinated double bond occupying the site trans to chloride. The eta(4)-bonding mode can be readily identified by the unusually high-field chemical shift associated with the phosphorus atom adjacent to the eta(2)-coordinated double bond. Complexes 2a, 2b, 4, and 5a form catalysts that are active for transfer hydrogenation of a range of ketones. In all cases, catalysts formed from precursors 2a and 2b are markedly more active than those formed from 4 and 5a.

  DOI：

  10.1021/om020861b
• 作为试剂：
  描述：

  对甲基苯甲酸甲酯 在 2-氨甲基吡啶 、 RuCl2(NBD)2(py)2 、 1,3-双(二苯基膦)丙烷 、 potassium tert-butylate 、 氢气 作用下， 以 2-甲基四氢呋喃 为溶剂， 50.0 ℃ 、5.0 MPa 条件下， 反应 16.0h， 以96%的产率得到(4-甲基苯基)甲醇
  参考文献：
  名称：

  便利和改进的协议，用于将Ru催化剂的酯从（P，P），（P，N，N）和（P，N，O）的配体衍生的氢化†往最‡

  摘要：

  报道了一种改进的方案，其中用配体处理前体[Ru（Cl）2（NBD）（Py）2 ]以形成用于酯加氢的[RuCl 2（二齿配体）（二胺）]预催化剂。在芳族酯的氢化中，已经研究了该催化剂家族以及三齿P ^ N ^ X（X = NR 2，OH）配体的钌配合物。一系列芳族酯可以在30°C至100°C的温度下高产率氢化。

  DOI：

  10.1039/c2dt30973d

文献信息

• “Pincer” Pyridine–Dicarbene–Iridium and ‐Ruthenium Complexes and Derivatives Thereof
  作者：Andreas A. Danopoulos、Pierre Braunstein、Jörg Saßmannshausen、David Pugh、Joseph A. Wright

  DOI：10.1002/ejic.202000429

  日期：2020.9.22

  experimental structures and rationalize their features. 1 undergoes oxidative transformations with CH2Cl2 to cis‐[IrIII(CNMeC)(CH2Cl)Cl2] (7) and with PhICl2 to mer‐[IrIII(CNMeC)Cl3] (8). The ruthenium derivatives trans‐[RuII(CNC)Cl2L] CNC = [2,6‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene]‐pyridine, L = pyridine, 10} and [RuII(CNC)(η2,η2‐nbd)](X)2 . 2L (nbd = 2,5‐norbornadiene, L = CH3CN, X = BF4 11), were

  阳离子钳型配合物[Ir I（CN Me C）L] X CN Me C = [2,6-双（2,6-二异丙基苯基）咪唑-2-亚基] -3,5-二甲基吡啶，L = CO，X = PF 6 4；L = CH 3 CN，X = PF 6 5；L =吡啶，X = BAr F 4，Ar F = 3,5-双三氟甲基-苯基6 }，是通过置换氯配体从[Ir I（CN Me C）Cl]（1）中获得的表征。配合物4和5采用方形平面，面内扭曲几何形状，而在6中金属环境呈显着的金字塔形。4和6中阳离子的理论计算重现了实验结构并使其特征合理化。1层进行氧化，用CH变换2氯2至顺式- [铱III（CN我C）（CH 2 Cl）的氯2 ]（7）中并用PhICl 2至聚体-的[Ir III（CN我C）氯3 ]（8）。钌衍生物反式[Ru II（CNC）氯2 L] CNC = [2,6-双（2,6-二异丙基苯基）咪唑-2-亚基]
• Preparation and structure elucidation of novel organoruthenium amidinates bearing η4-diene ligands
  作者：Taizo Hayashida、Kazuma Miyazaki、Yoshitaka Yamaguchi、Hideo Nagashima

  DOI：10.1016/s0022-328x(01)01150-0

  日期：2001.9

  A series of novel ruthenium amidinate complexes bearing η4-cyclooctadiene (COD) or η4-norbornadiene (NBD) ligand was prepared, and their structures were elucidated by spectroscopy and crystallography. A disilver amidinate, Ag2μ2,η-PhNC(H)NPh}2, was treated with either (η4-COD)Ru(MeCN)2Cl2 or (η4-NBD)Ru(pyridine)2Cl2 to form the corresponding bisamidinate complex, (η4-COD)Ruη2-PhNC(H)NPh}2 (5a)

  一系列新颖钌脒基络合物轴承η的4 -cyclooctadiene（COD）或η 4 -norbornadiene（NBD）配位体制备，其结构分别通过光谱法和结晶学阐述。甲脒disilver，银2 μ 2，η-PhNC（H）NPh} 2，用任一（η处理4 -COD）的Ru（MeCN中）2氯2或（η 4 -NBD）的Ru（吡啶）2 CL 2以形成相应的bisamidinate络合物，（η 4 -COD）茹η 2 -PhNC（H）NPh} 2（图5a）或（η 4 -NBD）茹η 2-PhNC（H）= NPh} 2（5a），分别具有中等至良好的产量。可替代地，（η 4 -COD）茹η 2 -我PRNC（Me）中N我镨} 2（图5b）或（η 4 -NBD）茹η 2 -我PRNC（Me）中N我镨} 2（图5b '）通过的反应合成[（η 4 -COD）的RuCl 2 ] ñ或（η 4 -NBD）的Ru（吡啶）2氯2与Li
• Asymmetric Hydrogenation of Ketones with Ruthenium Complexes of <i>rac</i>- and Enantiopure (<i>S</i>,<i>S</i>)-1,2-Bis((diphenylphosphino)methyl)cyclohexane:  A Comparative Study with <i>rac</i>- and (<i>R</i>)-BINAP
  作者：Simon Doherty、Julian G. Knight、Adam L. Bell、Ross W. Harrington、William Clegg

  DOI：10.1021/om070129i

  日期：2007.4.1

  Ruthenium(II) complexes of the type trans-[RuCl21,2-bis((diphenylphosphino)methyl)cyclohexane}(diamine)] based on the inexpensive and easy-to-prepare rac- and (S,S)-1,2-bis((diphenylphosphino)methyl)cyclohexane form highly active and enantioselective catalysts for the asymmetric hydrogenation of a wide range of aryl and heteroaryl ketones, in most cases giving ee's that exceed those obtained with

  基于便宜且易于制备的rac-和（S，S）-的反式-[RuCl 2 1,2-双（（二苯基膦基）甲基）环己烷}（二胺）]型钌（II）配合物1,2-双（（二苯基膦基）甲基）环己烷形成了高活性和对映选择性的催化剂，可用于广泛范围的芳基和杂芳基酮的不对称加氢反应，在大多数情况下，ee均超过其BINAP对应物所获得的ee。尽管基于1,2-双（（二苯基膦基）甲基）环己烷的预催化剂在溶液中缓慢异构化，以形成具有顺式氯化物排列的热力学上有利的异构体，但由两种异构体生成的催化剂具有相似的对映选择性。
• Ruthenium PCP–bis(phosphinite) pincer complexes
  作者：Robin B. Bedford、Michael Betham、Michael E. Blake、Simon J. Coles、Sylvia M. Draper、Michael B. Hursthouse、P. Noelle Scully

  DOI：10.1016/j.ica.2005.07.050

  日期：2006.4

  The reactions of [RuHCl(CO)(PPh3)(3)] with resorcinol bis(phosphinite) pincer ligands lead to complexes of the general formula [RuCl(PCP)(CO)(PPh3)]; the crystal structure of one example has been determined. The structures of the bulky resorcinol 2-methyl4,6-di-tert-butyl resorcinol and its mono-diisopropylphosphinite derivative were also determined. Reactions of [RuCl2(PPh3)(3)] with resorcinot bis(phosphinite) ligands yield complexes of the type [RuCl(PCP)(PPh3)], while the reaction of C6H-2-Me-4,6-'Bu-2-1,3-(OPPh2) with [RuHCl(CO)(PPh3)(3)] provides a PCP-pincer complex in which the ligand has undergone 2-methyl C-H activation. (c) 2005 Elsevier B.V. All rights reserved.