[Ru(=C=CH2)(1,2-bis(diphenylphosphino)ethane)Cp*]PF6 | 583884-55-3

• 英文名称: [Ru(=C=CH2)(1,2-bis(diphenylphosphino)ethane)Cp*]PF6
• 英文别名: [Ru(=C=CH₂)(1,2-bis(diphenylphosphino)ethane)Cp*]PF₆；[Ru(=C=CH₂)(dppe)Cp*]PF₆；[Ru(C=CH₂)(dppe)Cp*]PF₆；[Ru(=C=CH2)(dppe)Cp*][PF6]；[Ru(pentamethylcyclopentadienyl)(1,2-bis(diphenylphosphino)ethane)(CCH2)]PF6；[Ru(vinylidene)(dppe)(pentamethylcyclopentadienyl)][hexafluorophosphate]；[Ru(=C=CH2)(1,2-bis(diphenylphosphino)ethane)(η5-C5Me5)][PF6]
• CAS: 583884-55-3
• 化学式: C₃₈H₄₁P₂Ru*F₆P
• 分子量: 805.725
• InChiKey: XOVYCTRLHSMEAN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Ru(=C=CH2)(1,2-bis(diphenylphosphino)ethane)Cp*]PF6 在 t-BuOK 作用下， 以 四氢呋喃 为溶剂， 以95%的产率得到Ru(C≡CH)(dppe)Cp*
  参考文献：
  名称：

  Syntheses, Structures, and Spectro-electrochemistry of {Cp*(PP)Ru}C⋮CC⋮C{Ru(PP)Cp*} (PP = dppm, dppe) and Their Mono- and Dications

  摘要：

  The complexes {Cp*(PP)Ru}(2)(mu-Cequivalent toCCequivalent toC) (PP = dppm 5a, dppe 5b) have been synthesized from RuCl(PP)Cp* (1a/b) via the corresponding vinylidenes [Ru(=C=CH2)(PP)Cp*](+) (2a/b), deprotonation (KOBut) to the ethynyls Ru(Cequivalent toCH)(PP)Cp* (3a/b), oxidative coupling ([FeCp2][PF6]) to the bis(vinylidenes) [{Ru(PP)Cp*}2{mu-(=C=CHCH=C=)}](2+) (4a/b), and deprotonation [dbu (4a), KOBut (4b)]. Electrochemistry of 5a/b revealed the expected sequence of four le redox steps, which occurred at significantly lower Edegrees values than found for the Ru(PPh3)(2)Cp analogue. Single-crystal X-ray structure determinations are reported for 1a/b, 2a/b, 3a/b, 4a/b, and 5a/b, together with the oxidized products [5b] [PF6](n) (n = 1, 2). In the monocation [5b] [PF6] the Ru-C(l) [1.931(2) Angstrom] and C-C distances [1.248-1.338(3) Angstrom] are intermediate between those found in 5b and the dication [5b](2+). The short Ru-C [1.857(5) Angstrom] and experimentally equal C-C distances [1.269-1.280(6) Angstrom] in [5b] [PF6](2) confirm the anticipated dicarbene-cumulene structure for the Ru=C=C=C=C=Ru bridge.

  DOI：

  10.1021/om030015g
• 作为产物：
  描述：

  ammonium hexafluorophosphate 、 pentamethylcyclopentadienyl(1,2-bis(diphenylphosphino)ethane)chlororuthenium(II) 、 三甲基乙炔基硅 以 二氯甲烷 为溶剂， 以74%的产率得到[Ru(=C=CH2)(1,2-bis(diphenylphosphino)ethane)Cp*]PF6
  参考文献：
  名称：

  Syntheses, Structures, and Spectro-electrochemistry of {Cp*(PP)Ru}C⋮CC⋮C{Ru(PP)Cp*} (PP = dppm, dppe) and Their Mono- and Dications

  摘要：

  The complexes {Cp*(PP)Ru}(2)(mu-Cequivalent toCCequivalent toC) (PP = dppm 5a, dppe 5b) have been synthesized from RuCl(PP)Cp* (1a/b) via the corresponding vinylidenes [Ru(=C=CH2)(PP)Cp*](+) (2a/b), deprotonation (KOBut) to the ethynyls Ru(Cequivalent toCH)(PP)Cp* (3a/b), oxidative coupling ([FeCp2][PF6]) to the bis(vinylidenes) [{Ru(PP)Cp*}2{mu-(=C=CHCH=C=)}](2+) (4a/b), and deprotonation [dbu (4a), KOBut (4b)]. Electrochemistry of 5a/b revealed the expected sequence of four le redox steps, which occurred at significantly lower Edegrees values than found for the Ru(PPh3)(2)Cp analogue. Single-crystal X-ray structure determinations are reported for 1a/b, 2a/b, 3a/b, 4a/b, and 5a/b, together with the oxidized products [5b] [PF6](n) (n = 1, 2). In the monocation [5b] [PF6] the Ru-C(l) [1.931(2) Angstrom] and C-C distances [1.248-1.338(3) Angstrom] are intermediate between those found in 5b and the dication [5b](2+). The short Ru-C [1.857(5) Angstrom] and experimentally equal C-C distances [1.269-1.280(6) Angstrom] in [5b] [PF6](2) confirm the anticipated dicarbene-cumulene structure for the Ru=C=C=C=C=Ru bridge.

  DOI：

  10.1021/om030015g

文献信息

• Facile Decarboxylation of Propiolic Acid on a Ruthenium Center and Related Chemistry
  作者：John H. Bowie、Michael I. Bruce、Mark A. Buntine、Alexander S. Gentleman、David C. Graham、Paul J. Low、Gregory F. Metha、Cassandra Mitchell、Christian R. Parker、Brian W. Skelton、Allan H. White

  DOI：10.1021/om300157w

  日期：2012.8.13

  corresponding alkynyls. Attempted deprotonation of [Ru(═C═CH2)(dppe)Cp]+ with LiBu gave the binuclear cyclobutenylidinium complex [Ru(dppe)Cp}2(μ-C4H3)]+. The X-ray diffraction molecular structures of [Ru(dppe)Cp}2(μ-C4H3)]PF6 (11), [Ru═C(OMe)CH2(CO2Me)}(dppe)Cp]PF6 (13), RuC(OMe)═CH(CO2R)}(dppe)Cp (R ═ Me (15), Et (16)) and Ru(C≡CCO2R)(dppe)Cp (R = Me (21), Et (22)) are described.

  RC≡CCO的自发脱羧2 H（R = H，PH）发生在与的RuCl（PP）的Cp（PP =（PPH反应3）2，DPPE），得到的[Ru（═C═CHR）（PP）的Cp] +。可能的机制脱羧计算研究（DFT）表明，该反应导致CO的挤出2和形成的[Ru（═C═CH 2）（DPPE）的Cp] +最有可能是由阴离子HC≡CCO的初始相互作用发生2 -用的RuCl（DPPE）通过羧酸酯与Ru的协调的Cp，随后通过形成η的2 -alkyne中间体，其重排至η 1与CO的损失-乙炔基物种2。乙炔基的质子化得到母体亚乙烯基。相反，HC CCO 2 R（R = Me，Et）与RuCl（PP）Cp和[NH 4 ] PF 6在甲醇中的反应给出了[Ru ═C（OMe）CH 2（CO 2 R）} ]（PP）的Cp +，通过MeOH中的攻击中C形成α中间亚乙烯基的[Ru ═C═CH（CO的2 R）}（PP）的Cp]
• Synthesis and Some Reactions of the Heterometallic C₇ Complex {Cp*(dppe)Ru}C≡CC≡CC≡CC{Co₃(μ-dppm)(CO)₇}
  作者：Michael I. Bruce、Marcus L. Cole、Christian R. Parker、Brian W. Skelton、Allan H. White

  DOI：10.1021/om7010968

  日期：2008.7.1

  o3(μ-dppm)(CO)7}]OTf (5), while addition of tcne or tcnq across the central C≡C bond gave Cp*(dppe)Ru}C≡CC[═C(CN)2]C[═C(CN)2]C≡CCCo3(μ-dppm)(CO)7} (6) and Cp*(dppe)Ru}C≡CC[═C6H4C(CN)2]C[═C(CN)2]C≡CCCo3(μ-dppm)(CO)7} (7), respectively. The reaction between 1 and Fe2(CO)9 was more complex, the major product being Cp*(dppe)Ru}C≡CCFe3(CO)9}CC≡CCCo3(μ-dppm)(CO)7} (8), accompanied by an Fe2(CO)6 derivative

  通过涉及C 7组装的三种途径获得了异金属碳链络合物Cp *（DPPE）Ru}C≡CC≡CC≡CCCo 3（μ-DPPM）（CO）7 }（1）。通过适当的C 1 + C 6，C 2 + C 5或C 3 + C 4前体的组合形成链。Cp类似物2和Co 3（CO）9簇类似物3分别通过C 2 + C 5和C 1 + C 6途径获得。反应1用PPh 3取代，通过取代Co 3簇键合的CO基团得到4。将MeOTf加到1中Ru中心的第二个碳原子上得到亚乙烯基[Cp *（DPPE）Ru}═C═CMeC≡CC≡CCCo 3（μ-DPPM）（CO）7 }] OTf（5），而在中心C≡C键上添加tcne或tcnq则得到Cp *（DPPE）Ru}C≡CC[═C（CN）2 ] C [═C（CN）2 ]C≡CCCo 3（μ-DPPM）（CO）7 }（6）和的Cp *（DPPE）茹}C≡CC[= C 6 H
• Substitution of Tetracyanoethene by Ethynyl–Metal Complexes Gives Tricyanovinylethynyl (Tricyanobutenynyl) Derivatives: Syntheses, Protonation, and Addition of Metal–Ligand Fragments
  作者：Michael I. Bruce、Mark A. Fox、Paul J. Low、Brian K. Nicholson、Christian R. Parker、Wyona C. Patalinghug、Brian W. Skelton、Allan H. White

  DOI：10.1021/om2007503

  日期：2012.4.9

  hindered, the normal [2 + 2]-cycloaddition/ring-opened product MC[═C(CN)2]CH═C(CN)2}(PP)Cp′ also being formed in some cases. The diynyl complex Ru(C≡CC≡CH)(dppe)Cp* reacts with tcne to give only the ring-opened adduct RuC≡CC[═C(CN)2]CH═C(CN)2}(dppe)Cp*. Protonation (HBF4 or HPF6) of RuC≡CC(CN)═C(CN)2}(dppe)Cp* afforded the vinylidene cation [Ru═C═CHC(CN)═C(CN)2}(dppe)Cp*]+. A second transition-metal

  与乙炔基配合物M（C≡CH）反应后，通过将四氰基乙烯中的CN基团取代，获得了一系列含有新的三氰基乙烯基乙炔基（3,4,4-三氰基丁-3-烯-1-炔基）配体的配合物。 PP）Cp'（M = Ru，Os，（PP）Cp'=（PPh 3）2 Cp; M = Ru，PP = dppe，Cp'= Cp，Cp *）。随着金属环境变得更受空间阻碍，反应以更高的收率进行，通常的[2 + 2]-环加成/开环产物M C [═C（CN）2 ]CH═C（CN）2 }（PP在某些情况下也会形成Cp'。二炔基络合物Ru（C≡CC≡CH）（dppe）Cp *与tcne反应仅生成开环的加合物Ru C≡CC[═C（CN）2 ]CH═C（CN）2 }（dppe ）Cp *。质子化（HBF 4或HPF6）Ru C≡CC（CN）═C（CN）2 }（dppe）Cp *提供亚乙烯基阳离子[Ru ═C═CHC（CN）═C（CN）2
• The preparation, characterisation and electronic structures of 2,4-pentadiynylnitrile (cyanobutadiynyl) complexes
  作者：Sören Bock、Samantha G. Eaves、Matthias Parthey、Martin Kaupp、Boris Le Guennic、Jean-François Halet、Dmitry S. Yufit、Judith A. K. Howard、Paul J. Low

  DOI：10.1039/c3dt33052d

  日期：——

  Convenient preparative routes to mononuclear ruthenium complexes containing the 2,4-pentadiynylnitrile, or cyanobutadiynyl, ligand are described. The electronic properties of the [C5N]− ligand are closely related to those of not only the cyanide ([CN]−) and 2-propynylnitrile or cyanoacetylide ([CCCN]−) ligands, but also those of the isoelectronic polyynyl ([CC}nR]−) ligands.

  描述了含有2,4-戊二炔基腈或氰基丁二炔基配体的单核钌配合物的方便制备路线。 [C5N]− 配体的电子性质不仅与氰化物 ([CN]−) 和 2-丙炔腈或氰乙炔 ([CCCN]−) 配体的电子性质密切相关，而且与等电子聚炔基 ([ CC}nR]−) 配体。
• Syntheses, structural characterisation and electronic structures of some simple acyclic amino carbene complexes
  作者：Samantha G. Eaves、Dmitry S. Yufit、Brian W. Skelton、Judith A. K. Howard、Paul J. Low

  DOI：10.1039/c5dt01806d

  日期：——

  = Fe(dppe)Cp, Ru(dppe)Cp, Ru(PPh3)2Cp, Ru(dppe)Cp*]. Crystallographic, spectroscopic and computational data support a description of these complexes in terms of a M-C(Me)N+H2} mesomeric form, and simple σ-coordination of the singlet acyclic amino carbene.

  亚乙烯基配合物[M（C CH 2）（PP）Cp'] PF 6与NH 3的反应容易得到无环氨基卡宾配合物[M C（Me）NH 2 }（PP）Cp'] PF 6 [M （PP）Cp'＝ Fe（dppe）Cp，Ru（dppe）Cp，Ru（PPh 3）2 Cp，Ru（dppe）Cp *]。晶体学，光谱学和计算数据支持对这些配合物的M- C（Me）N + H 2 }介晶形式的描述，以及单线态无环氨基卡宾的简单σ配位。