cis-[RuCl2(1,2-bis(dicyclohexylphosphino)ethane)(2,2'-bipyridine)]

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: cis-[RuCl2(1,2-bis(dicyclohexylphosphino)ethane)(2,2'-bipyridine)]
• 英文别名: cis-[RuCl2(1,2-bis(dicyclohexylphosphino)ethane)(2,2'bipyridine)]；cis-[RuCl2(dcype)(bipy)]；Dichlororuthenium;dicyclohexyl(2-dicyclohexylphosphanylethyl)phosphane;2-pyridin-2-ylpyridine
• 化学式: C₃₆H₅₆Cl₂N₂P₂Ru
• 分子量: 750.778
• InChiKey: LZJPOTYVCUNGJC-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  12.8
• 重原子数：
  43
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ammonium hexafluorophosphate 、 亚硝酸钠-15N 、 cis-[RuCl2(1,2-bis(dicyclohexylphosphino)ethane)(2,2'-bipyridine)] 在 HCl 作用下， 以 盐酸 、 二氯甲烷 为溶剂， 生成 [RuCl((15)NO)(dcype)(bipy)](PF6)2
  参考文献：
  名称：

  New nitrosyl ruthenium complex [RuCl(NO)(dcype)(bipy)](PF6)2: Synthesis, electrochemistry, NMR and ESI-MS/MS studies

  摘要：

  Reactivity of cis-[RuCl2(dcype)(bipy)] (dcype = 1,2-bis(dicyclohexylphosphino)ethane and bipy = 2,2'-bipyridine) with nitric oxide afforded the new dicationic complex [RuCl(NO)(dcype)(bipy)](2+). The complex isolated as PF6- salt was characterized by spectroscopical, electrochemical and ESI-MS/MS techniques as well as elemental analysis. Surprisingly the analysis of P-31{H-1} and N-15{N-1} NMR spectra of the [RuCl((SNO)-S-15)(dcype)(bipy)](2+) complex reveal that the NO is in trans position to one of the P atom of dcype. The IR spectrum showed the presence of v(NO) in 1889 cm(-1) with is in agreement with the presence of NO+, but based on P-31{H-1} NMR analysis the nitrosyl do not behave as a strong pi-acceptor since little (or none) trans structural effect was observed on P-31 chemical shift compared to the precursor cis-[RuCl2(dcype)(bipy)]. In the ESI-MS analysis, we just have detected the intact nitrosyl complex in CH2Cl2 solutions, but in MeOH solutions, the ion [M-NO](+) was detected, indicating the lability of M-NO bond. MSn spectra with variable collision energy indicate a fragmentation pathway with radical bi-cyclohexyl-phosphine and two cyclohexene losses. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.inoche.2006.09.023
• 作为产物：
  描述：

  cis-[RuCl₂(PPh₃)2(bipy)] 、 1,2-双(二环己基磷基)-乙烷 以 二氯甲烷 为溶剂， 以94%的产率得到cis-[RuCl2(1,2-bis(dicyclohexylphosphino)ethane)(2,2'-bipyridine)]
  参考文献：
  名称：

  Ruthenium Phosphine/Diimine Complexes:  Syntheses, Characterization, Reactivity with Carbon Monoxide, and Catalytic Hydrogenation of Ketones

  摘要：

  The cis-[RuCl2(PPh3)(2)(N-N)] (N-N = bipy (1), Me-bipy (2), phen (3), and bathophen (4)) complexes were used to synthesize five new electron-rich phosphine-containing complexes cis- [RuCl2(dcype)(N-N)] (N-N = bipy (1a), Me-bipy (2a), phen (3a), and bathophen (4a)) and cis- [RuCl2(PEt3)(2)(bipy)] (1c) by phosphine exchange. These complexes were obtained and characterized by NMR (P-31{H-1}, H-1), cyclic voltammetry, and elemental analysis. Electrochemical studies of these complexes reveal a single reduction process (Ru-III/Ru-II). These complexes are more easily oxidized than their analogues cis-[RuCl2(dppb)(N-N)]. The reactivity of complexes cis-[RuCl2(dcype)(N-N)] with carbon monoxide was tested, and dissociation of one chloride was observed, leading to the formation of four new cationic species with general formula [RuCl(CO)(dcype)(N-N)](PF6) (bipy (1b), Me-bipy (2b), phen (3b), and bathophen (4b)). The complexes described here and elsewhere with general formulas cis-[RuCl2(P-P)(N-N)], [RuCl(CO)(dcype)(N-N)] (PF6) and cis-[RuCl2(P)(2)(N-N)] were used as precatalysts in the transfer hydrogenation of functionalized aryl-ketones, and most of them were active. X-ray structures of cis- [RuCl2(PEt3)(2)(bipy)] (1c) and [RuCl(CO)(dcype)(bipy)](PF6) (1b) will be presented.

  DOI：

  10.1021/om050182b

文献信息

• Observation of vinylidene emission in mixed phosphine/diimine complexes of Ru(II) at room temperature in solution
  作者：André L. Bogado、Rose M. Carlos、Cristina Daólio、Antonio G. Ferreira、Miguel G. Neumann、Frank Rominger、Sergio P. Machado、Juliana P. da Silva、Márcio P. de Araujo、Alzir A. Batista

  DOI：10.1016/j.jorganchem.2011.09.017

  日期：2012.1

  The mixed ruthenium(II) complexes trans-[RuCl2(PPh3)2(bipy)] (1), trans-[RuCl2(PPh3)2(Me2bipy)](2), cis-[RuCl2(dcype)(bipy)](3), cis-[RuCl2(dcype)(Me2bipy)](4) (PPh3 = triphenylphosphine, dcype = 1,2-bis(dicyclohexylphosphino)ethane, bipy = 2,2′-bipyridine, Me2bipy = 4,4′-dimethyl-2,2′-bipyridine) were used as precursors to synthesize the associated vinylidene complexes. The complexes [RuCl(CCHPh)(PPh3)2(bipy)]PF6

  混合钌（II）配合物反式-[RuCl 2（PPh 3）2（bipy）]（1），反式-[RuCl 2（PPh 3）2（Me 2 bipy）]（2），顺式-[RuCl 2（dcype）（bipy）]（3），顺式-[RuCl 2（dcype）（Me 2 bipy）]（4）（PPh 3  =三苯基膦，dcype = 1,2-双（二环己基膦基）乙烷，bipy = 2， 2′-联吡啶，Me 2联＝ 4，4′-二甲基-2，2′-联吡啶被用作前体来合成相关的亚乙烯基络合物。络合物[RuCl（C CHPh）（PPh3）2（bipy）] PF 6（5），[RuCl（C CHPh）（PPh 3）2（Me 2 bipy）] PF 6（6），[RuCl（C CHPh）（dcype）（bipy）] PF参照图6（7），对[RuCl（C CHPh）（dcype）（bipy）] PF 6（8）进行了表征，并检查了它们的光
• Ruthenium Phosphine/Diimine Complexes:  Syntheses, Characterization, Reactivity with Carbon Monoxide, and Catalytic Hydrogenation of Ketones
  作者：Márcio P. de Araujo、Alberthmeiry T. de Figueiredo、André L. Bogado、Gustavo Von Poelhsitz、Javier Ellena、Eduardo E. Castellano、Claudio L. Donnici、João V. Comasseto、Alzir A. Batista

  DOI：10.1021/om050182b

  日期：2005.12.1

  The cis-[RuCl2(PPh3)(2)(N-N)] (N-N = bipy (1), Me-bipy (2), phen (3), and bathophen (4)) complexes were used to synthesize five new electron-rich phosphine-containing complexes cis- [RuCl2(dcype)(N-N)] (N-N = bipy (1a), Me-bipy (2a), phen (3a), and bathophen (4a)) and cis- [RuCl2(PEt3)(2)(bipy)] (1c) by phosphine exchange. These complexes were obtained and characterized by NMR (P-31H-1}, H-1), cyclic voltammetry, and elemental analysis. Electrochemical studies of these complexes reveal a single reduction process (Ru-III/Ru-II). These complexes are more easily oxidized than their analogues cis-[RuCl2(dppb)(N-N)]. The reactivity of complexes cis-[RuCl2(dcype)(N-N)] with carbon monoxide was tested, and dissociation of one chloride was observed, leading to the formation of four new cationic species with general formula [RuCl(CO)(dcype)(N-N)](PF6) (bipy (1b), Me-bipy (2b), phen (3b), and bathophen (4b)). The complexes described here and elsewhere with general formulas cis-[RuCl2(P-P)(N-N)], [RuCl(CO)(dcype)(N-N)] (PF6) and cis-[RuCl2(P)(2)(N-N)] were used as precatalysts in the transfer hydrogenation of functionalized aryl-ketones, and most of them were active. X-ray structures of cis- [RuCl2(PEt3)(2)(bipy)] (1c) and [RuCl(CO)(dcype)(bipy)](PF6) (1b) will be presented.
• New nitrosyl ruthenium complex [RuCl(NO)(dcype)(bipy)](PF6)2: Synthesis, electrochemistry, NMR and ESI-MS/MS studies
  作者：Gustavo Von Poelhsitz、André Luiz Bogado、Gezimar Donizetti de Souza、Edson Rodrigues-Filho、Alzir Azevedo Batista、Márcio Peres de Araujo

  DOI：10.1016/j.inoche.2006.09.023

  日期：2007.2

  Reactivity of cis-[RuCl2(dcype)(bipy)] (dcype = 1,2-bis(dicyclohexylphosphino)ethane and bipy = 2,2'-bipyridine) with nitric oxide afforded the new dicationic complex [RuCl(NO)(dcype)(bipy)](2+). The complex isolated as PF6- salt was characterized by spectroscopical, electrochemical and ESI-MS/MS techniques as well as elemental analysis. Surprisingly the analysis of P-31H-1} and N-15N-1} NMR spectra of the [RuCl((SNO)-S-15)(dcype)(bipy)](2+) complex reveal that the NO is in trans position to one of the P atom of dcype. The IR spectrum showed the presence of v(NO) in 1889 cm(-1) with is in agreement with the presence of NO+, but based on P-31H-1} NMR analysis the nitrosyl do not behave as a strong pi-acceptor since little (or none) trans structural effect was observed on P-31 chemical shift compared to the precursor cis-[RuCl2(dcype)(bipy)]. In the ESI-MS analysis, we just have detected the intact nitrosyl complex in CH2Cl2 solutions, but in MeOH solutions, the ion [M-NO](+) was detected, indicating the lability of M-NO bond. MSn spectra with variable collision energy indicate a fragmentation pathway with radical bi-cyclohexyl-phosphine and two cyclohexene losses. (c) 2006 Elsevier B.V. All rights reserved.