dichlorotetrakis(triethyl phosphite)ruthenium(II) | 53433-15-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: dichlorotetrakis(triethyl phosphite)ruthenium(II)
• 英文别名: trans-[RuCl₂{P(OEt)₃}₄]；dichlororuthenium;triethyl phosphite
• CAS: 53433-15-1；111059-31-5
• 化学式: C₂₄H₆₀Cl₂O₁₂P₄Ru
• 分子量: 836.604
• InChiKey: APUZOKGTFZXIDU-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  10.67
• 重原子数：
  43.0
• 可旋转键数：
  28.0
• 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(triethyl phosphite)ruthenium(II) 、 tert-butyllithium 以 四氢呋喃 为溶剂， 以35%的产率得到trans-((t)Bu-C*C-)2-tetrakis(triethyl 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
• 作为产物：
  描述：

  水合三氯化钌 、 亚磷酸三乙酯 在 zinc 作用下， 以 乙醇 为溶剂， 以>=65的产率得到dichlorotetrakis(triethyl phosphite)ruthenium(II)
  参考文献：
  名称：

  阳离子亚磷酸钌（II）配合物。单羰基和异氰化物衍生物的制备和性质

  摘要：

  单和三µ-氯钌（II）配合物[Ru 2 Cl 3 L 8 ] BPh 4和[Ru 2 Cl 3 L 6 ] BPh 4 [L = P（OEt）3或P（OEt）2 Ph]通过使三氯化钌与亚磷酸酯在回流的乙醇中反应来制备。还通过含亚磷酸酯的RuCl 3的羰基化反应制备了反式-[RuCl（CO）L 4 ] +类型的阳离子羰基衍生物。解决方案。检查了所有这些化合物与异氰化物的反应，并合成了新的[RuCl（RNC）2 L 3 ] +，[Ru（RNC）3 L 3 ] 2+和[RuCl（CO）（RNC） L 3 ] +衍生物。还讨论了通过ir和1 H和31 P nmr数据表征络合物的方法。

  DOI：

  10.1039/dt9870001813
• 作为试剂：
  描述：

  二氧化碳 、 二乙胺 、 苯乙炔 在 dichlorotetrakis(triethyl phosphite)ruthenium(II) 作用下， 80.0 ℃ 、8.0 MPa 条件下， 反应 15.0h， 以74%的产率得到(Z)-β-<(diethylcarbamoyl)oxy>styrene
  参考文献：
  名称：

  NMR Observation of Trialkylphosphite-Palladium(II) and Ruthenium(II) Complexes in Supercritical Carbon Dioxide

  摘要：

  利用配备高压氧化锆池的商用核磁共振波谱仪开发了一种超临界流体核磁共振（scNMR）光谱方法，该方法揭示了三烷基亚磷酸配体对于提高二氯化钯（II）和二氯化钌（II）配合物在超临界二氧化碳（scCO2）中的溶解度非常有效。

  DOI：

  10.1246/cl.2002.424

文献信息

• Syntheses and molecular structures of trans-bis(alkynyl) tetrakis-triethylphosphite ruthenium complexes
  作者：Samantha G. Eaves、Brian W. Skelton、Paul J. Low

  DOI：10.1016/j.jorganchem.2017.04.028

  日期：2017.10

  A simple synthesis of complexes trans-[Ru(C≡CC6H4-4-R)2P(OEt)3}4] from trans-[RuCl2P(OEt)3}4] and the terminal alkyne is described. Crystallographically determined molecular structures indicate a range of conformers, with the ethynyl arylene rings differing in their orientation with respect to each other across the RuP(OEt)3}4 fragment. Electrochemical analysis reveals a well-behaved one-electron

  复合物的简单的合成反式的[Ru（C≡CC 6 ħ 4 -4-R）2 P（OET）3 } 4 ]从反式-将[RuCl 2 P（OET）3 } 4 ]与末端炔描述。晶体学确定的分子结构指示一系列构象异构体，其中乙炔基亚芳基环在整个Ru P（OEt）3 } 4片段上彼此之间的取向不同。电化学分析揭示了一个表现良好的单电子氧化过程，这是只有约100 mV的更积极的是，类似的反式的[Ru（C≡CC 6H 4 -4-R）2（dppe）2 ]络合物。量子化学计算揭示了很大程度上离域的电子结构，并表明这些化合物可能在单分子电子学中用作线状分子。
• Single-Molecule Conductance Studies of Organometallic Complexes Bearing 3-Thienyl Contacting Groups
  作者：Sören Bock、Oday A. Al-Owaedi、Samantha G. Eaves、David C. Milan、Mario Lemmer、Brian W. Skelton、Henrry M. Osorio、Richard J. Nichols、Simon J. Higgins、Pilar Cea、Nicholas J. Long、Tim Albrecht、Santiago Martín、Colin J. Lambert、Paul J. Low

  DOI：10.1002/chem.201604565

  日期：2017.2.10

  The compounds and complexes 1,4‐C6H4(C≡C‐cyclo‐3‐C4H3S)2 (2), trans‐[Pt(C≡C‐cyclo‐3‐C4H3S)2(PEt3)2] (3), trans‐[Ru(C≡C‐cyclo‐3‐C4H3S)2(dppe)2] (4; dppe=1,2‐bis(diphenylphosphino)ethane) and trans‐[Ru(C≡C‐cyclo‐3‐C4H3S)2P(OEt)3}4] (5) featuring the 3‐thienyl moiety as a surface contacting group for gold electrodes have been prepared, crystallographically characterised in the case of 3–5 and studied

  化合物和配合物 1,4-C 6 H 4 (C≡C- cyclo ‐3-C 4 H 3 S) 2 ( 2 ), trans -[Pt(C≡C- cyclo ‐3-C 4 H 3 S) ) 2 (PEt 3 ) 2 ] ( 3 ),反式-[Ru(C≡C-环-3-C 4 H 3 S) 2 (dppe) 2 ] ( 4 ; dppe=1,2-双(二苯基膦)乙烷）和反式‐[Ru(C≡C- cyclo ‐3-C 4 H 3 S) 2 P(OEt) 3 } 4 ] ( 5 ) 以 3-噻吩基部分作为金电极的表面接触基团，具有已制备，在3 – 5的情况下进行了晶体学表征，并通过使用扫描隧道显微镜断裂结 (STM-BJ) 和 STM- I ( s ) 方法（测量隧道电流 ( I ) 作为距离 ( s )的函数)。这些化合物表现出相似的电导曲线，其中低电导特征更容易通过 STM- I ( s ) 方法识别，而较高特征则通过
• Preparation of new acetylide and vinylidene complexes of ruthenium
  作者：Gabriele Albertin、Stefano Antoniutti、Emilio Bordignon、Manuel Granzotto

  DOI：10.1016/s0022-328x(99)00193-x

  日期：1999.8

  Monoacetylide RuCl(CCR)P4 complexes (R=Ph, 4-MeC6H4, 1,4-C6H4CCH, SiMe3, But or COOMe; P=P(OEt)3 or P(OMe)3) were prepared by allowing RuCl2P4 to react with terminal alkynes RCCH in the presence of an excess of NEt3. Dinuclear compounds [Ru[P(OEt)3]5}2(μ-1,4-CCC6H4CC)]Y2 (Y=PF6 or BPh4) were also prepared from the reaction of RuCl2P4 with 1,4-HCCC6H4CCH. Treatment of RuCl2P4 with Li+[1,4-HCCC6H4CC]−

  Monoacetylide的RuCl（CCR）p 4复合物（R = PH，4-MEC 6 ħ 4，1,4-C 6 H ^ 4 CCH，森达3，卜吨或COOMe; P = P（OET）3或P（OME）3）通过使制备的RuCl 2 P 4在过量净的存在下与末端炔烃RCCH反应3。双核化合物[茹[P（OET）3 ] 5 } 2（μ-1,4-CCC 6 ħ 4 CC） - ] Y 2（Y = PF 6或BPH 4）也从的RuCl反应制备2 P 4用1,4-二HCCC 6 ħ 4 CCH。的RuCl的治疗2 P 4与Li + [1,4-HCCC 6 ħ 4 CC] - ，得到双（炔基）的Ru（1,4-CCC 6 ħ 4 CCH）2 P 4〔 P = P（OEt）3，P（OMe）3或PPh（OEt）2 ]衍生物。单乙炔化物RuCl（CCR）P 4与CF 3 SO 3 H的质子化反应生成亚乙烯基[RuCl
• Evaluation of the 5-ethynyl-1,3,3-trimethyl-3H-indole ligand for molecular materials applications
  作者：David Jago、David C. Milan、Alexandre N. Sobolev、Simon J. Higgins、Andrea Vezzoli、Richard J. Nichols、George A. Koutsantonis

  DOI：10.1071/ch23069

  日期：——

  and [M(L)n] (M = Ru; (L)n = (dppe)2 or (P(OEt)3)4; or M = Pt; (L)n = (PEt3)2, (PPh3)2 or tricyclohexylphosphine, (PCy3)2) modified with a 5-ethynyl-1,3,3-trimethyl-3H-indole ligand were prepared and characterised by NMR spectroscopy, IR and single-crystal X-ray diffraction. Cyclic voltammetry and IR spectroelectrochemistry of the ruthenium systems showed a single-electron oxidation localised over the

  用有机金属部分对共轭有机化合物进行改性可以调节此类化合物的电子和光电性质，并使其具有多种材料应用。有机金属配合物 [M(Cp′)(L) n ] （M = Ru 或 Fe；Cp′ = 环戊二烯 (Cp) 或五甲基环戊二烯 (Cp*)；(L) n  = (PPh 3 ) 2或 1,2-双(二苯基膦)乙烷 (dppe)) 和 [M(L) n ] (M = Ru; (L) n  = (dppe) 2或 (P(OEt) 3 ) 4 ; 或 M = Pt; (L) n  = (PEt 3 ) 2 , (PPh 3 ) 2制备了用 5-乙炔基-1,3,3-三甲基-3 H-吲哚配体修饰的三环己基膦 (PCy 3 ) 2 ) ，并通过 NMR 光谱、IR 和单晶 X 射线衍射进行了表征。钌体系的循环伏安法和红外光谱电化学显示单电子氧化位于 M-C=C-芳基部分。吲哚配体的 N-杂原子表现出路易斯碱性质，能够从亚乙烯基中间体中提取质子并与
• The X-ray crystal structure and reactivity of trans-[RuCl2(P(OC2H5)3)4]
  作者：Selma Elaine Mazzetto、Maria Teresa do Prado Gambardella、Regina Helena Almeida Santos、Luiz Gonzaga de França Lopes、Douglas Wagner Franco

  DOI：10.1016/s0277-5387(98)00382-9

  日期：1999.2

  The X-ray structure of trans-[RuCl2(P(OC2H5)(3))(4)] indicates that the molecule has the C-2 symmetry with the Ru(II) and the two Cl ions lying on the two-fold axis. The E-Ru(III)/Ru(II)(O) in the trans-[RuCl2(P(OC2H5)(3))(4)] complex is 0.61+/-0.01 vs. SCE, (mu=0.10 M NaCF3COO/CF3COOH, ethanol/water 2:1, 25 degrees C, C-H(+)=1.0X10(-2) M). In the same experimental conditions the electronic spectrum of this complex exhibit two bands: 254 nm (epsilon congruent to 6.7X10(3) M-1 cm(-1)) and 410 nm (epsilon=8X10 M-1 cm(-1)) and a shoulder at 290 nm (epsilon congruent to 6X10(2) M-1 cm(-1)). Only one signal (128 ppm) is observed in the P-31 NMR spectrum of trans-[RuCl2(P(OC2H5)(3))(4)] in ethanol (130 ppm) or ethanol/water buffered solutions at pH = 7.0 (128 ppm), In ethanol or ethanol/water buffered solutions, the complex trans-[RuCl2(P(OC2H5)(3)](4), exhibits dissociation of two chloride ligands (k(-Cl)=(3.2+/-0.2)X10(-5) s(-1); 25 degrees C, mu=0.10 (NaCF3COO), yielding as a product the [Ru(P(OC2H5)(3))(4)S-2](2+) ion in which the two axial positions are occupied by solvent molecules (S). In the presence of acid, the final product is the cis-[Ru(P(OC2H5)(3))(2)S-4](2+) ion. (C) 1999 Elsevier Science Ltd. All rights reserved.