{RuCl2(2,2'-bis(diphenylphosphino)1,1'-binaphthyl)(PPh3)} | 144356-18-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: {RuCl2(2,2'-bis(diphenylphosphino)1,1'-binaphthyl)(PPh3)}
• 英文别名: RuCl2(2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)(PPh3)；dichloro(R-2,2'-bis(diphenylphosphine)-1,1'-binaphtyl)(triphenylphosphine)ruthenium(II)
• CAS: 144356-18-3；149197-45-5
• 化学式: C₆₂H₄₇Cl₂P₃Ru
• 分子量: 1056.95
• InChiKey: RIZBJBNXVLQHLO-UHFFFAOYSA-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(2,2'-bis(diphenylphosphino)1,1'-binaphthyl)(PPh3)} 、 苯甲腈 以 苯 为溶剂， 以91%的产率得到RuCl2(2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)(PhCN)2
  参考文献：
  名称：

  Chiral and Achiral Diphosphine Complexes of Ruthenium(II) Incorporating Labile Nitrile Ligands:  Synthesis and Solution Chemistry of Mono- and Dinuclear Derivatives of Ru₂Cl₄(PP)₂ (PP = Chelating Diphosphine)

  摘要：

  A family of nitrile complexes has been prepared by reaction of Ru2Cl4(PP)(2) Or RuCl2(PP)(PPh3) (PP = Ph2P(CH2)(4)PPh2 (dppb), Ph2PCH2CHOCMe2OCHCH2PPh2 (diop), 2,2'-bis(diphenylphosphino)-1, 1'-binaphthyl (binap)) with MeCN or PhCN, the product formed depending strongly on the reaction conditions. At high nitrile concentrations, the principal species present is RuCl(PP)(RCN)(3)X-+(-) (X = Cl); the cation can generally be isolated (as the PF6 salt) by abstraction of the chloride counterion with NH4PF6. Use of 2 equiv of NH4PF6 generates Ru(PP)(RCN)(4)(2+)(PF6-)(2) (PP = dppb). In the absence of a halide-abstracting agent, addition of hexanes or diethyl ether precipitates neutral RuCl2(PP)(RCN)(2) species, which undergo further loss of nitrile in the solid state (R = Me) or in solution (R = Me, Ph). Redissolution of the neutral species in chlorocarbon solvents gives Ru2Cl3(PP)(2)(RCN)(2)X-+(-) (X = Cl) and, in benzene, Ru2Cl4(PP)(2)(RCN). The dinuclear cation (X = PF6) is also accessible by reaction of RuCl(PP)(RCN)(3)+PF6- with CH2Cl2 or CDCl3, while the mononitrile can be obtained directly by reaction of Ru2Cl4(PP)(2) or RuCl2(PP)(PPh3) with small amounts of nitrile in benzene.

  DOI：

  10.1021/ic960735y

文献信息

• A Mechanism Displaying Autocatalysis:  The Hydrogenation of Acetophenone Catalyzed by RuH(<i>S</i>-binap)(app) Where app Is the Amido Ligand Derived from 2-Amino-2-(2-pyridyl)propane
  作者：Alen Hadzovic、Datong Song、Christina M. MacLaughlin、Robert H. Morris

  DOI：10.1021/om700849w

  日期：2007.11.1

  is achieved if 2-propanol is used as a solvent. This “alcohol effect” is favored by the pyridyl ligand app since it was not observed for the similar catalyst RuH(NHCMe2CMe2NH2)(binap). While 3 is an exceptional catalyst for H2-hydrogenation in 2-propanol (TOF > 6700 h-1 at 20 °C, 5 atm H2), it has a lower activity in transfer hydrogenation from the same solvent under comparable conditions (TOF 110 h-1

  已知2-（氨基甲基）吡啶（ampy）配体可活化钌配合物，用于酮的催化氢化。在这里，我们使用新的配体2-氨基-2-（2-吡啶基）丙烷（appH）制备定义明确的催化剂，以阐明吡啶基的作用。所述配体在α-碳上具有两个甲基以阻止β-氢化物消除反应。它与RuHCl（S -binap）（PPh 3）反应生成橙黄色的复合物RuHCl（S -binap）（appH）（2）。在强碱（KO t Bu）存在下，络合物2在温和条件下（20°C，5 atm H 2）转化为苯乙酮中H 2-加氢的活性催化剂）。2的溶液在氩气气氛下与KO t Bu迅速反应，生成深红色的酰胺基氢化物络合物RuH（S -binap）（app）（3），这是一种活性催化剂。晶体结构确定为3表示Ru-binap氢-酰胺基络合物的第一结构。它揭示了一个五坐标的Ru（II）中心，其Ru-N（酰胺基）距离短（1.962（3）Å），在酰胺氮上具有三角平面
• A remarkable temperature-dependent, accidental degeneracy of 31P NMR chemical shifts in Ru(ii) diphosphine/diimine complexes
  作者：Paul W. Cyr、Brian O. Patrick、Brian R. James

  DOI：10.1039/b103473c

  日期：——

  Several cis-RuX2((R)-BINAP)(diimine) complexes have been prepared, and many of these exhibit an unusual temperature-dependent, accidental degeneracy of the 31P shifts in their solution NMR spectra.

  我们制备了几种顺式-RuX2((R)-BINAP)(二亚胺)配合物，其中许多配合物在其溶液核磁共振光谱中表现出不寻常的温度依赖性和意外的 31P 位移变性。
• Synthesis, characterization and reactivity of some mono- and dinuclear chlororuthenium complexes containing chelating ditertiary phosphines (PP) with PP:Ru=1
  作者：Ajey M. Joshi、Ian S. Thorburn、Steven J. Rettig、Brian R. James

  DOI：10.1016/s0020-1693(00)92371-5

  日期：1992.8

  dppcp=Ph 2 P HPPh 2 ; dpcycp=(C 6 H 11 ) 2 P HP(C 6 H 11 ) 2 ; bdpp(skewphos)=Ph 2 PCH(Me)CH 2 CH(Me)PPh 2 ; binap=2,2′-bis(diphenylphosphine)-1,1′-binaphthyl; phenop=Ph 2 PN(Et)CH(CH 2 Ph)CH 2 OPPh 2 ; norphos=Ph 2 P HPPh 2 ). The [RuCl(binap)] 2 (μ-Cl) 2 species is also formed in solution by dissociation of PPh 3 from RuCl 2 (binap)(PPh 3 ) which is synthesized by phosphine exchange with RuCl 2 (PPh

  通过用H还原形成（PP）ClRu（μ-Cl）3 RuCl（PP）和[RuCl（PP）] 2（μ-Cl）2产物的混合价络合物2是合成的，其中PP是螯合的二叔膦Ph 2 P（CH 2）n PPh 2（n = 3-6）或一些相关的手性类似物，例如diop，chiraphos，dpPCp，dPCycp，bdpp，binap， phenop或norphos（diop = Ph 2 PCH 2 HCH 2 PPh 2; chiraphos = Ph 2 PCH（Me）CH（Me）PPh 2; dpPCp = Ph 2 P HPPh 2; dPCycp =（C 6 H 11）2 P HP（ C 6 H 11）2； bdpp（skewphos）= Ph 2 PCH（Me）CH 2 CH（Me）PPh 2； binap = 2,2'-双（二苯基膦）-1,1'-联萘基; phenop = Ph 2 PN（Et）CH（CH
• mer-[RuCl3(P–P)H2O] (P–P=dppb or diop) as a starting material for the synthesis of binuclear complexes. Crystallographic structures of [(dppb)ClRu–μ(Cl)3–RuCl(dppb)] and [(η6-C6H6)Ru–μ(Cl)3–RuCl(dppb)].
  作者：Márcio P. de Araujo、Eliana M.A. Valle、Javier Ellena、Eduardo E. Castellano、Eduardo N. dos Santos、Alzir A. Batista

  DOI：10.1016/j.poly.2004.09.028

  日期：2004.12

  The reactivity of the mer-[RuCl3(dppb)H2O] complex (1) with di-hydrogen shows that the products formed depend on the conditions of the reaction, i.e., solvents and presence or absence of a base. The new mixed-valence complexes [(diop)ClRu–(μ-Cl)3–RuCl(dppb)] (3), [(binap)ClRu–(μ-Cl)3–RuCl(dppb)] (4), [(PPh3)2ClRu–(μ-Cl)3–RuCl(dppb)] (6), [(dppn)ClRu–(μ-Cl)3–RuCl(dppb)] (7), [(P-ptol3)2ClRu–(μ-Cl)3–RuCl(dppb)]

  所述的反应性聚体-将[RuCl 3（DPPB）H 2 O]配合物（1）与二氢表明，所形成的产物取决于反应，即，溶剂和存在或不存在碱的条件。新的混合价络合物[（diop）ClRu–（μ-Cl）3 –RuCl（DPPB）]（3），[（binap）ClRu–（μ-Cl）3 –RuCl（DPPB）]（4）， [（PPh 3）2 ClRu–（μ-Cl）3 -RuCl（DPPB）]（6），[（dppn）ClRu–（μ-Cl）3 -RuCl（DPPB）]（7），[（P- ptol 3）2 ClRu–（μ-Cl）3-RuCl（DPPB）]（8），[（灰飞虱3）2 ClRu-（μ-Cl）的3 -RuCl（DPPB）]（9），[（η 6 -C 6 H ^ 6）RU-（μ-CL ）3 –RuCl（DPPB）]（11）和已知的混合价[[DPPB）ClRu–（μ-Cl）3 –RuCl（DPPB）]（5）和[（dio
• Triply-bridged diruthenium(II) 1,4-bis(diphenylphosphino)butane (dppb) and (R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (binap) complexes, including structural characterisation of [(dppb) ClRu(μ-D2O)-(μ-Cl)2RuCl(dppb)], [(η2-H2) (dppb)Ru(μ-Cl)3RuCl(dppb)] and the [(dppb)ClRu(μ-Cl)3RuCl(dppb)]− anion
  作者：Kenneth S. MacFarlane、Ian S. Thorburn、Paul W. Cyr、Daniel E.K.-Y. Chau、Steven J. Rettig、Brian R. James

  DOI：10.1016/s0020-1693(97)05833-7

  日期：1998.4

  Several triply-bridged diruthenium(II)(1,4-bis(diphenylphosphino)butane) complexes were synthesised and characterised by elemental analysis, UV-Vis, NMR and IR spectroscopies, The solid-state structures of [(dppb)ClRu(mu-D2O)(mu-Cl)(2)RuCl(dppb)] (1), [(eta(2)-H-2) (dppb)Ru(mu-Cl)(3)RuCl(dppb)] (2) and [TMP][(dppb)ClRu(mu-Cl)(3)RuCl(dppb)] (3) were established by X-ray crystallographic analyses (TMP=1,1,3-trimethyl-2,3-dihydroperimidinium; dppb = Ph2P(CH2)(4)PPh2). Crystals of 1.1.5C(6)D(6), 2.1.5C(7)D(8) and 3.2Me(2)CO.2H(2)O are all monoclinic, space groups P2(1)/c, P2(1)/n and C2/c, respectively, with Z=4: a=16.8681(6), b=13.3542(4), c=26.4966(7) Angstrom, beta=91.877(1)degrees for 1.1.5C(6)D(6); a = 19.8123(1), b=14.5246(2), c = 22.1803(1) Angstrom, beta=106.58(1)degrees for 2.1.5C(7)D(8); a=21.596(2), b=16.019(2), c=22.317(2) Angstrom, beta=106.15(1)degrees for 3.2Me(2)CO . 2H(2)O. The structures of 1 and 2 were salved by direct methods while 3 was solved by heavy atom methods and all were refined by full-matrix least-squares procedures to R-1 = 0.0433, 0.0612 and R = 0.039 (wR(2) = 0.0709 (1), 0.1178 (2)) for 7751, 6757 and 5237 reflections with I greater than or equal to 2 sigma(I) for 1 and 2 and I greater than or equal to 3 sigma(I) for 3, respectively, Complex I was also studied in the solid-state by P-31 CP/MAS NMR spectroscopy. The bromo- and iodo-analogues of 1 were prepared, and these three species were screened as catalysts for hydrogenation of aldimines. The complexes [H2NR2][RuCl(P-P)}(2)(mu-Cl)(3)] were synthesised by the addition of NR3 or [H2NR2]Cl to RuCl2(P-P)(PPh3), where P-P = dppb or (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (binap) and R =Et, n-Bu or n-Oct. The syntheses of [(DMA)(2)H][(PPh3)(2)ClRu(mu-Cl)(3)RuCl(PPh3)(2)], [(py)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] and [(C2H4)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] were also accomplished (DMA = N,N-dimethylacetamide; py = pyridine). (C) 1998 Elsevier Science S.A.