dichlorotetrakis(trimethyl phosphite)ruthenium(II) | 61818-04-0

• 分子结构分类: 有机化合物 - 有机磷化合物 - 亚磷酸三烷基酯
• 英文名称: dichlorotetrakis(trimethyl phosphite)ruthenium(II)
• 英文别名: Ru[P(OMe)₃]₄Cl₂；dichlororuthenium;trimethyl phosphite
• CAS: 61818-04-0；99096-00-1
• 化学式: C₁₂H₃₆Cl₂O₁₂P₄Ru
• 分子量: 668.282
• InChiKey: YDLWZKPLAIVWGW-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  5.99
• 重原子数：
  31.0
• 可旋转键数：
  16.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  110.76
• 氢给体数：
  0.0
• 氢受体数：
  12.0

反应信息

• 作为反应物：
  描述：

  dichlorotetrakis(trimethyl phosphite)ruthenium(II) 以 甲苯 为溶剂， 以88%的产率得到[bis(dimethylphosphanylmethyl)-methylsilyl]methyl-dimethylphosphane;dichlororuthenium;trimethylphosphane
  参考文献：
  名称：

  Oligophosphan-Liganden：XXXIII。分子内部的Spaltungen von sp 2-和sp 3 -CH-Bindungenan L 4 Ru 0 -Komplexrümpfenmit P（0 -C 6 H 4 PMe 2）3，N（CH 2 CH 2 PMe 2）3， MeP（CH 2 CH 2 CH 2 PMe 2）2 / PR 3和MeSi（CH 2 PMe 2）3 / PR 3 （R = Me，OMe）阿尔斯·斯蒂格利根登（Stützliganden）

  摘要：

  同时尝试通过用Na（Hg ）还原（pp 3）RuCl 2（1）来制备组成为（pp 3）RuH（Ar）（pp 3 = P（0 -C 6 H 4 PMe 2）3）的配合物）在苯，甲苯和二甲苯中的分离仍不成功，在室温下顺利进行了C 6 H 6中pp同系物（pp 3）OsCl 2（2）的钠汞齐还原，得到了（pp 3 OsH（C 6 H 5）（ 7）。氢化苯基衍生物（pp2）[（MeO）3 P] RuH（C 6 H 5）（13）和（sip 3）（Me 3 P）RuH（C 6 H 5）（14）（pp 2 = MeP（CH 2 CH 2 CH 2 PME 2）2，抿3 = MESI（CH 2 PME 2）3（PP）均类似地通过还原用Na（汞柱的苯溶液获得）2）[（MEO）3 P]的RuCl 2（5）和（抿3）（Me 3 P）RuCl 2（6）。在回流的苯中用钠汞齐处理（np 3）RuCl 2（3）（np

  DOI：

  10.1016/0022-328x(91)83050-e
• 作为产物：
  描述：

  水合三氯化钌 、 三甲氧基磷 在 NaBH₄ 作用下， 以45%的产率得到dichlorotetrakis(trimethyl phosphite)ruthenium(II)
  参考文献：
  名称：

  亚磷酸酯配体稳定的新型双（乙炔）和乙酰内酯-亚乙烯基钌（II）配合物的制备，结构和反应性

  摘要：

  Bis(alkynyl) complexes Ru(C=CR)(2)P-4 (1-3) (R = Ph, p-tolyl, (t)Bu; P = P(OMe)(3) (1), P(OEt)(3) (2), PPh(OEt)(2) (3)) were prepared by reacting RuCl2P4 with excess Li+ RC=C-, and a trans geometry was established both in solids (X-ray) and in solution. The reaction of these alkynyls (1-3) with electrophilic reagent depends on the nature of the phosphite ligand. Vinylidene-acetylide derivatives [Ru(C=CR){=C=C(R(1))R}P-4](+) (R(1) = H (4, 5), CH3 (7, 8), ArN=N (10), I (12), 2,3-(NO2)(2)C6H3S (14)) were prepared with P(OMe)(3) and P(OEt)(3) ligand by treatment of 1 and 2 with HBF4, CF(3)SO(3)Me, ArN2+BF4-, I-2, and 2,3-(NO2)(2)C6H3SCl, respectively. Instead, only the diazo- and iodovinylidenes [Ru(C=CR){=C=C(R(1))R}P-4](+) (R(1) = p-tolN=N (11), I (13)) were obtained with the PPh(OEt)(2) phosphite ligand. These vinylidene compounds were fully characterized by IR, H-1, P-31, and C-13 NMR spectra, and a single-crystal X-ray structure determination of complex [Ru(C=CPh){=C=C(Me)Ph)-{P(OEt)(3)}(4)]CF3SO3 (8a) is reported. The alkynyl-vinylidene [Ru(C=CR){=C=C(H)R}P-4](+) cations (4, 5) rearrange in solution to enynyl [Ru(eta(3)-RC(3)CHR)P-4](+) derivatives, and the reaction is inhibited by the presence of free alkyne. Kinetic data support a mechanism involving a pentacoordinate intermediate formed by loss of the vinylidene ligand. Substitution of the =C=C(H)R ligand by phosphite, isocyanide, and nitrile is easy in 4 and 5 and leads to [Ru(C=CPh){P(OMe)(3)}P-4](+) (17), [Ru(C=CPh)(p-tolNC)P-4](+) (18), and [Ru(p-tolCN)(2)P-4](2+) (19) (P = P(OEt)(3)), derivatives. Deprotonation with a base of the vinylidene ligand in 4 and 5, giving Ru(C=CR)(2)P-4, was also detected.

  DOI：

  10.1021/om00009a015

文献信息

• Syntheses and Crystal Structures of Disulfide-Bridged Binuclear Ruthenium Compounds:  The First UV−Vis, Raman, ESR, and XPS Spectroscopic Characterization of a Valence-Averaged Mixed-Valent Ru^IIISSRu^II Core
  作者：Kazuko Matsumoto、Takaya Matsumoto、Masaki Kawano、Hiroshi Ohnuki、Yushi Shichi、Toshikazu Nishide、Toshio Sato

  DOI：10.1021/ja950391v

  日期：1996.1.1

  Disulfide-bridged binuclear ruthenium complexes, [RuCl(P(OMe)3)2}2(μ-Cl)2(μ-S2)] (1), [RuCl(P(OMe)3)2}(μ-Cl)2(μ-S2)Ru(CH3CN)(P(OMe)3)2]+ ([2]+), [Ru(CH3CN)3(P(OMe)3)2}2(μ-S2)]3+ ([3]3+), [Ru(CH3CN)(P(OMe)3)2}2(μ-Cl)2(μ-S2)]2+ ([4]2+), and [Ru(CH3CN)3(P(OMe)3)2}2(μ-S2)]4+ ([5]4+), have been synthesized, and their crystal structures have been solved. Compounds 1, [2]+, and [4]2+ have a triply bridged

  二硫桥双核钌配合物，[RuCl(P(OMe)3)2}2(μ-Cl)2(μ-S2)](1)，[RuCl(P(OMe)3)2}(μ -Cl)2(μ-S2)Ru(CH3CN)(P(OMe)3)2]+ ([2]+), [Ru(CH3CN)3(P(OMe)3)2}2(μ -S2)]3+ ([3]3+), [Ru(CH3CN)(P(OMe)3)2}2(μ-Cl)2(μ-S2)]2+ ([4]2+ ), 和 [Ru(CH3CN)3(P(OMe)3)2}2(μ-S2)]4+ ([5]4+), 已经合成，并解析了它们的晶体结构。化合物 1、[2]+ 和 [4]2+ 具有三重桥连的 RuIII (μ-Cl)2(μ-S2)RuIII 核心，其中 S22- 配体以顺式构型桥接两个 Ru 原子。化合物 [3]3+ 和 [5]4+ 具有单桥连的反式 RuSSRu 核心，其中 [3]3+ 对应于 [5]4+
• Catalytic reaction of methanol with a series of ruthenium(II) complexes and the mechanism of the formation of acetic acid from methanol alone
  作者：Tetsu Yamakawa、Masayuki Hiroi、Sumio Shinoda

  DOI：10.1039/dt9940002265

  日期：——

  ruthenium(II) complexes containing zero, one and two SnCl3– ligands, [RuCl2P(OMe)3}4]1, [RuCl(SnCl3)P(OMe)3}4]2 and [Ru(SnCl3)2P(OMe)3}3]3, have been compared in the reaction of methanol to form acetic acid (and/or methyl acetate due to esterification), as well as their reactions with the possible intermediates (formaldehyde, methyl formate) in the overall reaction. It was found that the formation of acetic

  一系列钌（的催化能力II包含零，一和二的SnCl）络合物3 -配位体，将[RuCl 2 P（OME）3 } 4 ] 1，将[RuCl（的SnCl 3）P（OME）3 } 4 ] 2和[Ru（SnCl 3）2 P（OMe）3 } 3 ] 3在甲醇反应生成乙酸（和/或由于酯化作用而生成的乙酸甲酯）的反应中，以及在整个反应过程中它们与可能的中间体（甲醛，甲酸甲酯）的反应之间进行了比较。发现仅由3发生由甲醇形成乙酸，其还将多聚甲醛或甲酸甲酯转化为乙酸。配合物1仅表现出Tischenko型二聚反应的催化活性（2HCHO→HCO 2 Me），复合物2表现出中间特性，能够催化两个反应（2HCHO→HCO 2 Me，HCO 2 Me→MeCO 2H），但无法与甲醇反应。根据甲醇与3的反应动力学结果，提出了一种可能的反应途径，其中甲醛竞争地共享一个共同的反应路径，从而形成甲酸甲酯和乙酸。对于甲酸甲酯作
• Studien zur CH-aktivierung
  作者：H. Werner、J. Gotzig

  DOI：10.1016/0022-328x(85)80013-9

  日期：1985.3

  MCl2(PMe3)nL4-n with AgPF6. Their UV spectra exhibit a characteristic CT band. [RuCl2(PMe3)4]PF6 and [OsCl2(PMe3)4]PF6 react with CO and P(OMe)3 by reduction to form the corresponding ruthenium(II) and osmium(II) compounds MCl2(PMe3)nL4-n.

  复合物的反式-MCl 2（PME 3）4（M =钌，锇）与CO和P（OME）反应3，得到单-和二取代衍生物反式，聚体-MCl 2（PME 3）3 L（L = CO，P（OME）3）和全反式-MCl 2（PME 3）2 [P（OME）3 ] 2分别。在反式-RuCl 2 [P（OMe）3 ] 4与CO和PMe 3的反应中，这些化合物反式，聚体-RuCl 2 [P（OME）3 ] 3（CO）和反式，顺式，顺-RuCl 2（PME 3）2 [P（OME）3 ] 2的合成。通过M（PMe 3）2 [P（OMe）3 ] 2 }作为中间体在苯或甲苯中用Na / Hg还原MCl 2（PMe 3）2 [P（OMe）3 ] 2导致随后的分子间芳烃和芳基（氢）金属配合物的顺式，反式，顺式-MH（C 6）的加成H 5）（PMe 3）2 [P（OMe）3 ] 2（M = Ru，Os）和MH（C 6 H 4 CH
• Organometallic Molecular Wires with Thioacetylene Backbones, <i>trans</i> ‐{RS‐(C≡C) _<i>n</i> } ₂ Ru(phosphine) ₄ : High Conductance through Non‐Aromatic Bridging Linkers
  作者：Atsushi Yashiro、Yuya Tanaka、Tomofumi Tada、Shintaro Fujii、Tomoaki Nishino、Munetaka Akita

  DOI：10.1002/chem.202100828

  日期：2021.7.2

  In this work, the design, synthesis, and single-molecule conductance of ethynyl- and butadiynyl-ruthenium molecular wires with thioether anchor groups [RS=n-C6H13S, p-tert-Bu−C6H4S), trans-RS−(C≡C)n}2Ru(dppe)2 (n=1 (1R), 2 (2R); dppe: 1,2-bis(diphenylphosphino)ethane) and trans-(n-C6H13S−C≡C)2RuP(OMe)3}4 3hex] are reported. Scanning tunneling microscope break-junction study has revealed conductance

  在这项工作中，设计、合成和单分子电导与硫醚锚定基团的乙炔基和丁二炔基钌分子线 [RS= n -C 6 H 13 S, p - tert -Bu-C 6 H 4 S) ,反式-RS−(C≡C) n } 2 Ru(dppe) 2 ( n =1 ( 1 R ), 2 ( 2 R ); dppe: 1,2-双(二苯基膦基)乙烷) 和反式-( n -C 6 H 13 S−C≡C) 2 RuP(OMe) 3} 4 3 hex ] 报告。扫描隧道显微镜断裂结研究表明，具有硫乙炔骨架的有机金属分子线的电导率高于具有芳基乙炔基钌与硫锚定基团反式- p -MeS-C 6 H 4 -(C ≡C) n } 2 Ru(膦) 4 4 n (n=1, 2) 和反式-(Th-C≡C) 2 Ru(膦) 4 5 (Th=3-噻吩基)。应该指出的是，由丁二炔线2构成的分子结R , trans - Au -RS-(C≡C)
• Organometallic molecular wires as versatile modules for energy-level alignment of the metal–molecule–metal junction
  作者：Kaho Sugimoto、Yuya Tanaka、Shintaro Fujii、Tomofumi Tada、Manabu Kiguchi、Munetaka Akita

  DOI：10.1039/c6cc01705c

  日期：——

  Organometallic Ru molecular wires show significantly higher conductance compared to their organic counterpart due to high-lying HOMOs.

  有机金属Ru分子导线与它们的有机对应物相比，由于高能HOMO，显示出显著更高的导电性。