Ru(III)(CCPh)(dppe)Cp* | 113152-57-1

• 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: Ru(III)(CCPh)(dppe)Cp*
• 英文别名: Ru(CCC₆H₅)(dppe)Cp*；[(η5-C5Me5)(η2-dppe)Ru(C2C6H5)]；Ru(CCPh)(dppe)Cp*；2-diphenylphosphanylethyl(diphenyl)phosphane;ethynylbenzene;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;ruthenium(2+)
• CAS: 113152-57-1
• 化学式: C₄₄H₄₄P₂Ru
• 分子量: 735.851
• InChiKey: URPHCMKRVLTGRH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.82
• 重原子数：
  47
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ferrocenium hexafluorophosphate 、 Ru(III)(CCPh)(dppe)Cp* 以 二氯甲烷 为溶剂， 生成 [Ru(III)(CCPh)(dppe)Cp*]PF6
  参考文献：
  名称：

  Iron and Ruthenium σ-Polyynyls of the General Formula [{M(dppe)Cp*}–(C≡C)_n–R]^0/+ (M = Fe, Ru): An Experimental and Theoretical Investigation

  摘要：

  Two series of metal-polyynyl complexes of iron and ruthenium of general formula [{M(dppe)Cp*}-(C C)(n)-R](0/+) (M = Fe, Ru; R = H, Ph, SiMe3, Au(PPh3); n = 1-3), have been synthesized, characterized, and theoretically analyzed. The results provide a comprehensive description of the effect of the length of the conjugated carbon chain and the role of the nature of the metal atom and the terminal substituent on their neutral and oxidized states. For the latter, the spin density found on the carbon chain is a source of instability; e.g., for R = Au(PPh3), the oxidized compounds are much more accessible electrochemically than the rest of the series but are susceptible to radical attack. Of particular interest is the use of joint experimental and theoretical EPR studies, which allow elucidation of the differences of behavior within the two series. It reveals that the atomic spin density on the metal is not a sufficient criterion to evaluate EPR anisotropy but that the specific nodal properties of the frontier spin-orbitals highly influence the EPR components. The localization of the spin density on specific carbon atoms of the conjugated chain (even numbered) opens up the possibility of building extended systems by targeted radical reactions.

  DOI：

  10.1021/om300584u
• 作为产物：
  描述：

  [Ru{C=C(H)C₆H₅}(dppe)Cp*]Cl 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 为溶剂， 以0.073 g的产率得到Ru(III)(CCPh)(dppe)Cp*
  参考文献：
  名称：

  铁与钌：半三明治第8组乙炔化物配合物的合成，结构和IR光谱电化学表征

  摘要：

  一种方便的修改对于络合物[M（C的制备所建立的合成路线CR）（DPPE）的Cp']（M =铁，钌; CP'=η 5 -C 5 H ^ 5（CP），η 5 -C 5 Me 5（Cp *）； R = C 6 H 5，C 6 H 4 - p -OMe，C 6 H 4 - p -NO 2，t Bu）和[Ru（C CR）（PPh 3）2 Cp ]从相应的[的MC1（PP）的Cp']配合物和炔烃HC CR经由描述了中间体亚乙烯基。通常从反应混合物中直接以高质量结晶样品的形式获得配合物。与先前的研究一致，铁络合物主要经历了以金属为中心的氧化，而乙炔配体更多地参与了与钌类似物有关的氧化过程。氧化还原性质的分析和光谱电化学研究表明，在Fe和Ru系列中，Cp与Cp *衍生物的总电子结构存在有限的差异。

  DOI：

  10.1039/d0nj03093g

文献信息

• Transition metal alkynyl complexes by transmetallation from Au(CCAr)(PPh₃) (Ar = C₆H₅or C₆H₄Me-4)
  作者：Wan M. Khairul、Mark A. Fox、Natasha N. Zaitseva、Maryka Gaudio、Dmitry S. Yufit、Brian W. Skelton、Allan H. White、Judith A. K. Howard、Michael I. Bruce、Paul J. Low

  DOI：10.1039/b809960j

  日期：——

  Facile acetylide transfer reactions take place between gold(I) complexes Au(CCAr)(PPh3) (Ar = C6H5 or C6H4Me-4) and a variety of representative inorganic and organometallic complexes MXLn (M = metal, X = halide, Ln = supporting ligands) featuring metals from groups 8–11, to afford the corresponding metal–alkynyl complexes M(CCR)Ln in modest to good yield. Reaction products have been characterised by

  金（I）配合物Au（C CAr）（PPh 3）（Ar = C 6 H 5或C 6 H 4 Me-4）与各种代表性的无机和有机金属配合物MXL n（M =金属，X =卤化物，L n =支持配体）以8-11族金属为特征，以中等到良好的收率得到相应的金属-炔基络合物M（CCR）L n。反应产物已通过分光光度法进行了表征，并报道了Fe（C CC 6 H 4 Me-4）（dppe）Cp，Ru（C CC 6 H 4 Me-4）（dppe）Cp *，Ru的分子结构测定（C CC 6 ˚F 5）（η 2 -O 2）（PPH 3）的Cp *，IR（C CC 6 H ^ 4 ME-4）（η 2 -O 2）（CO）（PPH 3）2，镍（ CCC 6 H 4 Me-4）（PPh 3）Cp和反式-Pt（C CAr）2 L 2（Ar = C 6 H 5，L = PPh 3 ; Ar = C 6 H 4 Me-4，L =
• Synthetic and electrochemical studies on alkynyl complexes of iron and ruthenium
  作者：Caroline Bitcon、Mark W. Whiteley

  DOI：10.1016/0022-328x(87)85198-7

  日期：1987.12

  Cyclic voltammetric studies on a series of alkynyl complexes [M(CCR)L2(η- C5R′5)] (M = Fe or Ru; R = Ph, Bun or But; L = CO or P-donor ligand; R′ = H or Me) reveal a one-electron oxidation at a glassy carbon electrode in dichloromethane. The chemical reversibility of the oxidation process is dependent upon all four variables (M, L, R and W) considered in this investigation.

  上的一系列炔基配合物的[M（CCR）L-循环伏安研究2（η-ç 5 R' 5 R = PH，卜;）]（M = Fe或钌ñ或卜吨; L = CO或P -供体配体； R'= H或Me）在二氯甲烷中的玻璃碳电极处显示单电子氧化。氧化过程的化学可逆性取决于此研究中考虑的所有四个变量（M，L，R和W）。
• Bonding and Substituent Effects in Electron-Rich Mononuclear Ruthenium σ-Arylacetylides of the Formula [(η²-dppe)(η⁵-C₅Me₅)Ru(C⋮C)-1,4-(C₆H₄)X][PF₆]<i>_n</i> (<i>n</i> = 0, 1; X = NO₂, CN, F, H, OMe, NH₂)
  作者：Frédéric Paul、Benjamin G. Ellis、Michael I. Bruce、Loic Toupet、Thierry Roisnel、Karine Costuas、Jean-François Halet、Claude Lapinte

  DOI：10.1021/om050799t

  日期：2006.1.1

  This study reports the isolation and the structural (X-ray), UV-vis, and NMR characterization of a series of electron-rich Ru(II) acetylide complexes of the formula (eta(2)-dppe)(eta(5)-C5Me5)Ru(C equivalent to X)-1,4-(C6H4)X (1a-f; X = NO2, CN, F, H, OMe, NH2) and (eta(2)-dppe)(eta(5)-C5Me5)Ru(C equivalent to C)-1,3-(C6H4)F (1c-m), as well as the spectroscopic (near-IR and ESR) in situ characterization of the corresponding elusive Ru(III) radical cations. The spectroscopic data are discussed in connection with DFT computations, and a consistent picture of the electronic structure of these Ru(11) and Ru(111) acetylide complexes is proposed. Notably, the strong reactivity of the Ru(Ill) radicals evidenced in this contribution constitutes a major difference with the relative stability of the known iron analogues.