| 56586-92-6

• CAS: 56586-92-6；15709-75-8
• 化学式: C₅₄H₄₅Br₂P₃Ru
• 分子量: 1047.75
• InChiKey: SUBOYUHMEGJJAF-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  12.02
• 重原子数：
  60.0
• 可旋转键数：
  12.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  、 1,4-双(二苯基膦)丁烷 以 further solvent(s) 为溶剂， 以97%的产率得到RuBr2(1,4-bis(diphenylphosphino)butane)(PPh3)
  参考文献：
  名称：

  X射线衍射和固态（31）P CP / MAS NMR研究表征五配位钌（II）膦配合物及其与亚砜和硫醚的反应性。

  摘要：

  检查31P CP / MAS NMR光谱作为表征固态钌（II）膦配合物的方法，并将结果与​​为RuCl（2）（dppb）（PPh（3））确定的X射线晶体学数据进行比较）（dppb = Ph（2）P（CH（2））（4）PPh（2）），RuBr（2）（PPh（3））（3）和先前确定的RuCl（2）（PPh（3） ））（3）。RuBr（2）（PPh（3））（3）（C（54）H（45）Br（2）P（3）Ru）的晶体为单斜晶，空间群P2（1）/ a，a = 12.482 （4）Å，b = 20.206（6）Å，c = 17.956（3）Å，beta = 90.40（2）度，Z = 4，以及RuCl（2）（dppb）（PPh（3）） （C（46）H（43）Cl（2）P（3）Ru）也是单斜的，空间群P2（1）/ n，a = 10.885（2）Å，b = 20.477（1）Å，c = 18.292（2）Å，β=

  DOI：

  10.1021/ic960860+

文献信息

• Halide-bridged arsine- and phosphine-capped diruthenium complexes, [(R3As)3Ru(μ-X)3Ru(AsR3)3]+ and [(R3P)3Ru(μ-X)3Ru(PR3)3]+ (X = Cl or Br), as precursors to confacial mixed-valence ruthenium ‘blues’: spectroelectrochemical studies spanning the binuclear oxidation states II,II, II,III and III,III
  作者：Brett D. Yeomans、David G. Humphrey、Graham A. Heath

  DOI：10.1039/a705675c

  日期：——

  A series of six tertiary-arsine-capped binuclear complexes, [L3Ru(µ-X)3RuL3][CF3SO3] (L = AsMe3, AsMe2Ph or AsMePh2; X = Cl or Br) together with a full range of purely PR3-capped analogues and the mixed-ligand complex [(Ph3P)(Me3As)2Ru(µ-Cl)3Ru(AsMe3)2(PPh3)][CF3SO3] have been characterised. The previously neglected arsine-capped compounds share the well defined electrochemical behaviour of their phosphine congeners. Stepwise reversible oxidations connect the Ru2II,II closed-shell d6d6 (=12-e) resting state with the d5d6 (11-e) and d5d5 (10-e) levels, and all the mixed-valence [L3Ru(µ-X)3RuL3]2+ species can be characterised through electrogeneration in CH2Cl2 at –60 °C. Unexpectedly, the Ru2II,III arsine complexes strongly resemble the classical ruthenium ‘blues’ where L = NH3 or H2O. For such valence-delocalised systems the visible region ordinarily contains an intense σ → σ* band (the source of the intense blue colour) together with a much weaker, near-infrared δπ* → σ* band. Bonding within the RuX3Ru}2+ core can then be monitored directly by νσ→σ*. The distinctly different spectral appearance of the more familiar PR3-capped mixed-valence compounds has been a long-standing puzzle, but the twenty electrogenerated 11-e binuclear systems assembled here with various AsR3 or PR3 terminal ligands are all delocalised, and clearly belong within a continuum of electronic behaviour with steadily decreasing metal–metal interaction. In all, νσ→σ* declines over a considerable range from 17 000 to below 5000 cm–1, with the ligands ranked as follows: L = NH3 (and 1,4,7-trimethyl-1,4,7-triazacyclononane) > H2O > Cl, Br (i.e. nonahalides) > AsR3 > PR3 and µ-Cl > µ-Br. These changes are well correlated with systematic trends in the g∥ and g⊥ components of the axial g tensor, and also with the gap between the stepwise oxidation potentials which shrinks from 1.2 to 0.45 V. For the PR3 complexes the decrease in νσ→σ* is accompanied by progressive intensity transfer to the δπ* → σ* band. The anticipated Ru · · · Ru separation is of the order of 2.9 and 3.0 Å for the mixed-valence AsMe3/µ-Cl and PMe3/µ-Cl systems respectively, markedly longer than the crystallographic value of 2.75 Å in [(NH3)3Ru(µ-Cl)3Ru(NH3)3]2+. The geometric distinction between the AsR3- and PR3-capped dimers is an unexpected consequence of selective crowding between the substituent R groups and the µ-X3} array. The present Ru2II,III systems are electronically distinct from their PR3-containing osmium counterparts, such as [(Et3P)3Os(µ-Cl)3Os(PEt)3]2+, which show still greater visible/near-infrared spectral deviations.

  一系列由次胂基封端的双核配合物, [L3Ru(µ-X)3RuL3][CF3SO3] (L = AsMe3, AsMe2Ph 或 AsMePh2; X = Cl 或 Br), 以及一系列纯由 PR3 封端的类似物和混合配体配合物 [(Ph3P)(Me3As)2Ru(µ-Cl)3Ru(AsMe3)2(PPh3)][CF3SO3] 已被表征。之前被忽视的胂基封端配合物与他们的膦同类物具有良好的电化学行为。分步可逆氧化过程将 Ru2II,II 闭壳层 d6d6 (=12-e) 基态与 d5d6 (11-e) 和 d5d5 (10-e) 能级连接起来, 所有混合价态的 [L3Ru(µ-X)3RuL3]2+ 物种都可以通过在 CH2Cl2 中于 -60 °C 下电化学产生来表征。出乎意料的是, Ru2II,III 胂配合物与经典的钌 "蓝" 配合物 (其中 L = NH3 或 H2O) 非常相似。对于这种价态离域的系统, 可见光区域通常包含一个强烈的 σ → σ* 带 (产生强烈的蓝色) 以及一个较弱的近红外 δπ* → σ* 带。 RuX3Ru}2+ 核心的键合可以通过 νσ-σ* 直接监测。更熟悉的 PR3 封端混合价态配合物的截然不同的光谱外观长期以来一直是一个谜, 但这里组装的二十个电化学产生的 11-e 双核系统, 与各种 AsR3 或 PR3 终端配体都是离域的, 并且显然属于电子行为的连续统, 金属-金属相互作用逐渐减弱。所有 νσ-σ* 从 17000 到低于 5000 cm-1 都有明显的下降, 配体排序如下: L = NH3 (以及 1,4,7-三甲基-1,4,7-三氮杂环壬烷) > > Cl, Br (即非卤化物) > AsR3 > PR3 以及 µ-Cl > µ-Br。这些变化与轴向 g 张量的 g‖ 和 g⊥ 分量中的系统性趋势很好地相关, 并且与分步氧化电位的间隙从 1.2 缩小到 0.45 V 也很好地相关。对于 PR3 配合物, νσ-σ* 的减少伴随着逐渐向 δπ* → σ* 带的强度转移。预期的 Ru···Ru 分离大约为 2.9 和 3.0 Å 分别对应 AsMe3/µ-Cl 和 PMe3/µ-Cl 混合价态系统, 明显长于 [(NH3)3Ru(µ-Cl)3Ru(NH3)3]2+ 中的晶体学值 2.75 Å。 AsR3- 和 PR3- 封端的二聚体在几何上的区别是由于取代基 R 组和 µ-X3} 阵列之间的选择性拥挤产生的意外后果。当前的 Ru2II,III 系统在电子上与包含 PR3 的锇同类物不同, 例如 [(Et3P)3Os(µ-Cl)3Os(PEt)3]2+, 它们在可见/近红外光谱上的偏差更大。
• Ruthenium-catalysed oxidation of allyl alcohols by molecular oxygen
  作者：Masakatsu Matsumoto、Satoru Ito

  DOI：10.1039/c39810000907

  日期：——

  Ruthenium(II) catalyses the homogeneous oxidation of allyl alcohols to carbonyl compounds by molecular oxygen under mild conditions.

  钌（II）在温和的条件下通过分子氧将烯丙醇均相氧化为羰基化合物。
• Generation of Stable Ruthenium(IV) Ketimido Complexes by Oxidative Addition of Oxime Esters to Ruthenium(II): Reactivity Studies Based on Electronic Properties of the Ru−N Bond
  作者：Takuya Shimbayashi、Kazuhiro Okamoto、Kouichi Ohe

  DOI：10.1002/chem.201704102

  日期：2017.11.27

  O‐chelating coordination to the Ru center prior to N−O bond cleavage. The obtained Ru ketimido complex could be transformed into a ruthenacycle by C−H activation by a concerted metalation–deprotonation mechanism in dichloromethane/methanol. Ru ketimido complexes with a tethered alkyne or alkene moiety underwent chloroamination of unsaturated C−C bonds followed by C−H activation, which resulted in the formation

  肟酯与[Ru（PPh 3）3 X 2 ]的反应在室温下平稳进行，得到稳定的Ru IV酮亚胺基络合物作为氧化加合物。X射线晶体学分析明确确定了络合物的结构，该分析显示了几乎线性的Ru-N-C阵列。氮原子的电子性质通过DFT计算估算，结果表明Ru-N键具有双键特性。动力学研究和对取代基对肟酯的影响的考虑导致提出了一种涉及氧化加成的反应机理的提议，该机理可以通过在N-O键断裂之前与Ru中心进行N，O-螯合配位而进行。可以通过在二氯甲烷/甲醇中的协同金属化-去质子化机理通过CH活化将获得的Ru ketimidoido络合物转变为钌环。具有连接的炔烃或烯烃部分的Ru ketimido配合物经历了不饱和C-C键的氯胺化，然后进行CH-H活化，从而导致了钌环的形成。考虑到孤立的Ru ketimido配合物的LUMO，氯胺化应通过同步的1,3-偶极环加成型机理进行。深入了解Ru ketimido配合物的特性和反应性将有助于肟酯催化转化的发展。
• New complexes of ruthenium (II) and (III) with triphenylphosphine, triphenylarsine, trichlorostannate, pyridine and other ligands
  作者：T.A. Stephenson、G. Wilkinson

  DOI：10.1016/0022-1902(66)80191-4

  日期：1966.4

  The interaction of triphenylphosphine, -arsine and -stibine with hydrated ruthenium trichloride in methanol leads to a variety of complexes such as [RuCl2(PPh3)4], [RuCl2(PPh3)3], [RuCl3(PPh3)2CH3OH], [RuCl3(AsPh3)2CH3OH] and [RuCl2(SbPh3)3]. The corresponding bromo complexes are also described. New mono and dicarbonyl complexes of ruthenium (II) and (III) have also been prepared by the interaction

  三苯基膦，-s和-二苯乙烯与甲醇中的水合三氯化钌的相互作用导致形成多种络合物，例如[RuCl 2（PPh 3）4 ]，[RuCl 2（PPh 3）3 ]，[RuCl 3（PPh 3）2 CH 3 OH]，[RuCl 3（AsPh 3）2 CH 3 OH]和[RuCl 2（SbPh 3）3]。还描述了相应的溴配合物。还已经通过Ph 3 P，Ph 3 As，Ph 3 Sb，吡啶等与含羰基溶液的相互作用制备了钌（II）和（III）的新的单和二羰基配合物。描述了顺式和反式-[RuCl 2（CO）2 L 2 ]，[RuCl 2（CO）L 3 ]和[pyH] [RuCl 4 COpy]的配合物。
• 2,2,3,4,4-pentamethylphosphetanic acid, C8H16PO2H: salts, complexes and a hydrogen bonded amine adduct
  作者：John Emsley、Amanda P. Dunning、Robert J. Parker、John K. Williams、Shirley Brown、Stella Earnshaw、David S. Moore

  DOI：10.1016/s0277-5387(00)88116-4

  日期：1984.1

  The conjugate base of the title acid, i.e. C8H16PO2−, has been investigated as its simple salts, as a ligand in transition metal complexes of cobalt and ruthenium, and as a secondary amonium salt in which hydrogen bonding between anion and cation occurs.

  标题酸的共轭碱，即，C 8 ħ 16 PO 2 - ，已被研究作为其简单的盐，如钴和钌的过渡金属配合物的配体，和作为二次amonium盐，其中氢键阴离子和之间阳离子发生。