Ru(H)(η(5)-indenyl)(bis(diphenylphosphino)methane) | 199189-25-8

• 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(H)(η(5)-indenyl)(bis(diphenylphosphino)methane)
• 英文别名: Ruthenium(II)(η5-indenyl)hydride[bis(diphenylphosphino)methane]；(η5-indenyl)(1,1'-bis(diphenylphosphanyl)methane)hydridoruthenium(II)；[RuH(η5-C9H7)(dppm)]；ruthenium(II) hydride(η5-indenyl)(dppm)；[RuH(η5-indenyl)(κ2-P-bis(diphenylphosphino)methane)]；(indenyl) [1,2-bis(diphenylphosphino)methane]ruthenium hydride；[RuH(η5-C9H7)(bis(diphenylphosphino)methane)]；RuH(dppm)(η5-C9H7)；diphenylphosphanylmethyl(diphenyl)phosphane;1H-inden-1-ide;ruthenium(1+) monohydride
• CAS: 199189-25-8
• 化学式: C₃₄H₃₀P₂Ru
• 分子量: 601.63
• InChiKey: NOKBHOVNZPWEQS-UHFFFAOYSA-N

计算性质

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

• 作为反应物：
  描述：

  Ru(H)(η(5)-indenyl)(bis(diphenylphosphino)methane) 、 1-乙炔-1-环庚醇 以 甲苯 为溶剂， 以70%的产率得到Ru(η(5)-indenyl)(bis(diphenylphosphino)methane)((E)-CH=CH-C=CH-(CH2)5)
  参考文献：
  名称：

  通过质子加成到乙烯基烯基衍生物上的区域选择性合成茚基钌（II）乙烯基亚烷基络合物

  摘要：

  Vinylalkenyl络合物的[Ru {（É）-CH CHCR CH 2 }（η 5 -C 9 ħ 7）（DPPM）]（DPPM =双（二苯基膦基）甲烷; R = H（1A），CH 3（图1b））和（ñ = 1（图2a），2（图2b），3（图2c））已经制备由氢化物络合物[期RuH（η的区域选择性和立体选择性的反应5 -C 9 ħ 7）（DPPM）]与炔丙醇HC⋮CC（OH）RCH 3（R = H，CH 3）和环状醇。反应进行通过在钌氢化物键导致瞬态羟基乙烯基配合物的[Ru {（醇的区域选择性和立体选择性插入ë）-CH CHC（OH）RCH 3 }（η 5 -C 9 ħ 7）（ dppm）]，然后进行快速脱水以得到最终产品。的羟基烯复杂的[Ru {（É）-CH CHCH 2 OH}（η 5 -C 9 ħ 7）（DPPM）]（3A）足够朝向脱水稳定的，可以从插入反应中分离[期RuH（η 5

  DOI：

  10.1021/om980300d
• 作为产物：
  描述：

  [(η6-indene)(hydrido)(((C6H5)2P)2CH2)ruthenium]CF3SO3 在 (C₂H₅)3N 作用下， 以 氘代四氢呋喃 为溶剂， 生成 Ru(H)(η(5)-indenyl)(bis(diphenylphosphino)methane)
  参考文献：
  名称：

  Protonation of η⁵-Indenyl Ruthenium Hydride Complexes (η⁵-C₉H₇)Ru(L₂)H and η⁵−η⁶ Haptotropic Rearrangement. X-ray Crystal Structures of (η⁵-C₉H₇)Ru(dppm)H and [(η⁶-C₉H₈)Ru(dppp)H]⁺

  摘要：

  Protonation of indenyl complexes (eta(5)-C9H7)Ru(dppm)H and (eta(5)-C9H7)Ru(PPh3)(2)H with CF3-SO3H or HBF4. Et2O at -60 degrees C gives the eta(2)-dihydrogen complex [(eta(5)-C9H7)Ru(dppm)(H-2)](+) and the dihydride [(eta(5)-C9H7)Ru(PPh3)(2)H-2](+), respectively. Upon warming to room temperature, proton shift from the eta(2)-H-2 ligand of the former to the indenyl ligand and subsequent migration of the metal fragment from the five-membered ring to the six-membered ring of the indene Ligand results in the formation of the eta(6)-indene complex [(eta(6)-C9H8)Ru(dppm)H](+). The PPh3 analogue[(eta(6)-C9H8)Ru(PPh3)(2)H](+) is formed in a similar fashion, but in this case, the proton shift is from Ru-H to the indenyl ligand. Low-temperature acidification of (eta(5)-C9H7)Ru(dppe)H and (eta(5)-C9H7)Ru(dppp)H yield mixtures of eta(2)-dihydrogen complex and dihydride in both cases. Similar to the dppm and PPh3 analogues, eta(6)-indene complexes [(eta(6)-C9H8)Ru(dppe)H](+) and [(eta(6)-C9H8)Ru(dppp)H](+) are generated upon warming solutions of the eta(2)-dihydrogen complex/dihydride mixtures to room temperature. In the dppp system, the eta(5) --> eta(6) haptotropic rearrangement only occurs after the eta(2)-dihydrogen complex --> dihydride tautomerization is nearly completed, whereas in the dppe system the two processes seem to occur simultaneously. The parent hydride complexes (eta(5)-C9H7)Ru(L-2)H can be regenerated upon deprotonation of the eta(6)-indene complexes with Et3N. Crystal structures of (eta(5)-C9H7)-Ru(dppm)H and [(eta(6)-C9H8)Ru(dppp)H](+) have been determined by X-ray crystallography; both complexes have three-legged piano-stool structures.

  DOI：

  10.1021/om000266e

文献信息

• Insertion Reactions of Alkynes into the Ru−H Bond of Indenylruthenium(II) Hydride Complexes. Mechanism of the Reaction of Phenylacetylene with [RuH(η<b>⁵</b>-C₉H₇)(dppm)] (dppm = Bis(diphenylphosphino)methane)
  作者：Mauro Bassetti、Paolo Casellato、M. Pilar Gamasa、José Gimeno、Covadonga González-Bernardo、Blanca Martín-Vaca

  DOI：10.1021/om970489d

  日期：1997.12.1

  α-metalated alkenyl complexes [RuC(CO2Me)CH2}(η5-C9H7)LL‘] (LL‘ = dppe, dppm; L = L‘ = PMe2Ph; L = PPh3, L‘ = PMe3) in refluxing diethyl ether. A kinetic study has been carried out for the reaction of the complexes [RuX(η5-C9H7)(dppm)] with phenylacetylene in toluene, by 1H and 31P1H} NMR spectroscopy. The reactions are first order with respect to the ruthenium complex and to the alkyne. The hydride and

  茚基配合物[RUX（η 5 -C 9 ħ 7）（DPPM）]（DPPM =双（二苯基膦基）甲烷，X = H，d）用苯乙炔反应，得到的产物顺式加成的[Ru （ë） - CH CXPh}（η 5 -C 9 ħ 7）（DPPM）]在甲苯中，在温度范围40-80℃。茚基配合物[期RuH（η 5 -C 9 ħ 7）LL ']（L = L'= PME 2 Ph值; L = PPH 3，L '= PME 2 Ph值; L = PPH 3，L'= PME 3 ; LL” = DPPE）和[期RuH（η 5 -Me 3 ç9 ħ 4）（CO）（PPH 3）]和环戊二烯基配合物[期RuH（η 5 -C 5 H ^ 5）（DPPM）]不与光子晶体⋮CH发生反应，即使在更加强制的条件。的配合物[期RuH（η 5 -C 9 ħ 7）LL ']（LL'= DPPE; LL '= DPPM; L = L'= PME 2
• Synthetic, X‐ray Diffraction, Electrochemical, and Density Functional Theoretical Studies of (Indenyl)ruthenium Complexes Containing Dithiolate Ligands
  作者：Sin Yee Ng、Jialin Tan、Wai Yip Fan、Weng Kee Leong、Lai Yoong Goh、Richard D. Webster

  DOI：10.1002/ejic.200700070

  日期：2007.8

  respectively (at a scan rate of 100 mV/s), at about 0 V versus Fc/Fc+. Complex 13 underwent additional one-electron oxidation processes at +0.5 and +0.8 V versus Fc/Fc+. The new complexes have all been characterized spectroscopically, and some (four containing the indenyl ligand and three of the non-indenyl type) by X-ray diffraction as well. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany

  复合物的卤化物取代 [(Ind)Ru(L2)X] Ind = η5-C9H7。1: (L2) = dppf [1,1'-双（二苯基膦基）二茂铁]，X = Cl；2：(L2) = dppm [1,1'-双(二苯基膦基)甲烷]，X = Cl；和 18: (L2) = (CO)2, X = I} 带有 1,1-二硫醇盐 –S2CNR2（二烷基二硫代氨基甲酸酯，R = Me、Et 和 C5H10），–S2COR（烷基黄原酸酯，R = Et 和 iPr ) 和–S2PR2（R = Et 和Ph 的二硫代次膦酸盐）表明茚基配体的不稳定性受共配体和进入的二硫醇盐以及溶剂的性质影响。除了二硫醇衍生物外，这些反应还以溶剂和化学计量相关的产率产生氢化物 [(Ind)Ru(diphos)H]。观察到的 Ind 不稳定性对 (L2) 的依赖性遵循顺序，dppf 黄原酸盐），与实验结果一致。发现茚基配体在氯取代 1
• η5-Indenylruthenium(II) hydride complexes: synthesis and protonation reactions
  作者：M.Pilar Gamasa、J Gimeno、Covadonga González-Bernardo、B.M Martı́n-Vaca、Javier Borge、Santiago Garcı́a-Granda

  DOI：10.1016/s0020-1693(02)01457-3

  日期：2003.4

  Hydride complexes [RuH(η5-1,2,3-C9R3R′4)LL′] (R=R′=H, LL′=dppm (1), dppe (2); L=L′=PMe2Ph (3); L=PPh3, L′=PMe3 (4), PMe2 Ph (5), PMePh2 (6); L=CO, L′=PiPr3 (7); R=Me, R′=H, LL′=dppm (8); L=CO, L′=PPh3 (9), PiPr3 (10); R=R′=Me, L=CO, L′=PiPr3 (11)) have been prepared by the reaction of complexes [RuX(η5-1,2,3-C9R3R′4)LL′] (X=Cl, Br) with an excess of NaOMe in methanol (reflux or room temperature). Protonation

  氢化物配合物[RuH（η5-1,2,3-C9R3R'4）LL']（R = R'= H，LL'= dpPM（1），dppe（2）; L = L'= PMe2Ph（3） ; L = PPh3，L'= PMe3（4），PMe2 Ph（5），PMePh2（6）; L = CO，L'= PiPr3（7）; R = Me，R'= H，LL'= dpPM（ 8）； L ＝ CO，L′＝ PPh 3（9），PiPr 3（10）； R ＝ R′＝ Me，L ＝ CO，L′＝ PiPr 3（11））是通过配合物[RuX（ η5-1,2,3-C9R3R'4）LL']（X = Cl，Br）和过量的NaOMe的甲醇溶液（回流或室温）。在Et2O中用HBF4·OEt2将氢化物络合物[RuH（η5-C9H7）（PPh3）L]（L = PPh3（12），PMe3（4））质子化，生成二氢化物络合物[RuH2（η5- ）（PPh3）
• Synthesis and electrochemical properties of bimetallic η⁵-indenyl ruthenium complexes
  作者：Quan Yuan Hu、Guochen Jia

  DOI：10.1139/v08-106

  日期：2009.1.1

  Treatment of RuCl(dppm)(η⁵-C₉H₇) with alkynes HC≡C(C₆H₄)_nC≡CH (n = 1, 2) in the presence of TlPF₆ and t-BuONa affords the bimetallic ruthenium acetylide complexes [(η⁵-C₉H₇)(dppm)Ru]₂(µ-C≡C(C₆H₄)_nC≡C). Reactions of the hydride complex RuH(dppm)(η⁵-C₉H₇) with HC≡C(C₆H₄)_nC≡CH (n = 1, 2) in refluxing toluene give the bimetallic ruthenium alkenyl complexes [(η⁵-C₉H₇)(dppm)Ru]₂(µ-CH=CH(C₆H₄)_nCH=CH). The electrochemical properties of the new complexes have been investigated by cyclic voltammetry, which reveals that the organic spacer –CH=CHC₆H₄CH=CH– is more effective than –C≡CC₆H₄C≡C– in mediating electronic communication between the two ruthenium moieties.Key words: ruthenium, bimetallic, acetylide, insertion, electrochemistry.

  在 TlPF6 和 t-BuONa 存在下，将 RuCl(dppm)(η5-C9H7)与炔烃 HC≡C(C6H4)nC≡CH (n = 1, 2) 处理，可得到双金属钌乙酰络合物 [(η5- )(dppm)Ru]2(µ-C≡C( )nC≡C)。氢化物配合物 RuH(dppm)(η5- )与 HC≡C( )nC≡CH (n = 1, 2)在回流甲苯中发生反应，得到双金属钌烯基配合物[(η5- )(dppm)Ru]2(µ-CH=CH( )nCH=CH)。通过循环伏安法研究了这些新配合物的电化学性质，结果表明，有机间隔物 -CH=CH CH=CH- 比 -C≡C C≡C- 在介导两个钌分子之间的电子通信方面更为有效。
• Synthesis and Properties of the Indenyl Ruthenium(II) Complex [Ru{(<i>E</i>)-η¹-C(C⋮CPh)CHPh}(η⁵-C₉H₇)(<i>κ</i>²-<i>P</i>-dppm)] (dppm = bis(diphenylphosphino)methane). An Organometallic Intermediate in the Catalytic Dimerization of Phenylacetylene
  作者：Mauro Bassetti、Silvia Marini、Josefina Díaz、M. Pilar Gamasa、José Gimeno、Yolanda Rodríguez-Álvarez、Santiago García-Granda

  DOI：10.1021/om020483a

  日期：2002.10.1

  The σ-enynyl complex 3 is protonated with an equimolar amount of HBF4·Et2O to give the cationic alkynylalkylidene complex [RuC(C⋮CPh)CH2Ph}(η5-C9H7)(κ2-P-dppm)][BF4] (4), which in turn is deprotonated by tBuOK to regenerate quantitatively complex 3. Both complexes 3 and 4 have been characterized by X-ray structural analysis. Complex 3 catalyzes the dimerization of PhC⋮CH to give (E)- and (Z)-1,4-

  [期RuH（η氢化物络合物的反应5 -C 9 ħ 7（）κ 2 - P- DPPM）]（1）与过量的1,4-二苯基-1,3-丁二炔，光子晶体⋮C-C ⋮器CPh，产生复杂的[Ru （ë）-η 1 -C（C⋮CPH）CHPh配合}（η 5 -C 9 ħ 7）（κ 2 - P- DPPM）]（3），通过区域选择性形成和炔在甲苯或苯-d 6中的Ru-H键立体选择性插入。该反应中，大于与末端炔苯乙炔慢4倍左右，通过缔合机理，其特征在于由下面的激活参数进行：Δ ħ ⧧ = 11千卡摩尔- 1 ; Δ小号⧧ = -44 CAL摩尔- 1 ķ - 1。的σ-enynyl复杂3与HBF等摩尔量的质子化4 ·的Et 2 O操作得到阳离子alkynylalkylidene复杂的[Ru C（Ç⋮CPH）CH 2博士}（η 5 -C 9 ħ 7）（κ 2 - P- DPPM）] [BF[4 ]（4），它又被t