2-dimethylphosphanylethyl(dimethyl)phosphane;ethene;ruthenium | 67421-25-4

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: 2-dimethylphosphanylethyl(dimethyl)phosphane;ethene;ruthenium
• CAS: 67421-25-4
• 化学式: C₁₄H₃₆P₄Ru
• 分子量: 429.405
• InChiKey: LFCMCYXLHZBEST-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：

  2-dimethylphosphanylethyl(dimethyl)phosphane;ethene;ruthenium 、 苯基膦 以 四氢呋喃 为溶剂， 以89.4%的产率得到cis-(Me2PCH2CH2PMe2)2Ru(PPhH)(CH2CH3)
  参考文献：
  名称：

  Reactions of (PMe3)4Ru(C2H4) and (DMPE)2Ru(C2H4) with Weak Proton-Donating Electrophiles HX (X = OAr, SAr, NHPh, PHPh). Synthesis of Complexes with Metal-Heteroatom Single Bonds

  摘要：

  Reactions of the ruthenium ethylene complexes (PMe(3))(4)Ru(C2H4) and (DMPE)(2)Ru(C2H4) with a variety of HX compounds (X = SAr, OAr, PPhH, NHPh and Ph) have been explored. In all cases; the tetrakis(trimethylphosphine) complex reacted to form ethylene and the hydride species, (PMe(3))(4)Ru(H)(X). However, parallel studies with the related material (DMPE)(2)Ru(C2H4) suggest that these complexes react as strained metallacycles toward HX. Thus, the bis(DMPE) analog gave the ethyl species (DMPE)(2)Ru(X)(CH2CH3) in its reactions with HSAr and PH(2)Ph, and thermolysis of these ethyl complexes led to the formation of the hydrides and free ethylene. The reaction of the DMPE ethylene complex with p-cresol allowed isolation of an intermediate cationic ethylene hydride species, but this was converted rapidly to the corresponding aryloxy hydride complex, even at room temperature. With NH(2)Ph the bis(DMPE) complex formed only the corresponding hydride species. In an attempt to generate an acetylene complex that similarly might react as a strained metallacyclopropene, (PMe(3))(4)Ru(CH=CH2)(2) was generated from the reaction of CH=CH2MgBr with (PMe(3))(4)RuCl2. However, thermolysis of the divinyl species led only to the formation of the butadiene complex, (PMe(3))(3)Ru(C4H6).

  DOI：

  10.1021/om00001a023
• 作为产物：
  描述：

  乙烯 、 cis-Ru[(CH₃)2PCH₂CH₂P(CH₃)2]2H₂ 以 氘代苯 为溶剂， 以>99的产率得到2-dimethylphosphanylethyl(dimethyl)phosphane;ethene;ruthenium
  参考文献：
  名称：

  铁族金属的氢化膦配合物的光化学

  摘要：

  在光解作用下，顺式[MH 2（DMPE）2 ]（M = Fe，Ru; Os; DMPE = Me 2 PCH 2 CH 2 PMe 2）和顺式[MH 2（DPPE）2 ]（M = Fe，Ru，Os Os； DPPE ＝ Ph 2 PCH 2 CH 2 PPh 2）通过两个氢原子的协同偶联容易失去H 2。光反应生成具有极强反应性的中间体[M（DMPE）2 ]和[M（DPPE）2 ]，它们与四氰基乙烯（TCNE）反应形成金属（II）配合物：[C 2（CN）3 M（DMPE）2 CN]，[C 2（CN）3 M（DPPE）2 CN]通过自由基氧化加成工艺。在路易斯配体L（例如[LM（DMPE）2 ]，[LM（DPPE）2 ]； L = CO，C 2 H 4）存在下，通过辐照标题化合物，可捕获反应性物质，得到零价化合物。。

  DOI：

  10.1016/0022-328x(86)84045-1

文献信息

• Nitrous Oxide Mediated Synthesis of Monomeric Hydroxoruthenium Complexes. Reactivity of (DMPE)₂Ru(H)(OH) and the Synthesis of a Silica-Bound Ruthenium Complex
  作者：Anne W. Kaplan、Robert G. Bergman

  DOI：10.1021/om980295d

  日期：1998.11.1

  to produce (DMPE)2Ru(H)(OC(O)CF3) (22, 55% yield). Much of the observed reactivity of 1 is rationalized using the assumption that the first step involves reversible formation of a metal cation/OH- ion pair (23). Attempts to trap the cation with ethylene resulted in formation of the ruthenium ethylene complex (DMPE)2Ru(C2H4) (2); there is strong evidence that 2 forms via a cationic hydridoruthenium ethylene

  用1当量的N 2 O处理（DMPE）2 Ru（H）2，以41％的收率得到氢氧钌络合物（DMPE）2 Ru（H）（OH）（1）。用过量的N 2 O进行进一步处理以30％的产率得到二羟基配合物（DMPE）2 Ru（OH）2（5）。酚，硫醇，和硅烷醇的除了1个产率相应的aryloxo-，thiolato-和siloxoruthenium络合物6 - 10在25-75％的产率。的羟配体1也可以与二氧化硅表面硅烷醇交换，以形成氧化硅结合的复合物（DMPE）2Ru（H）（OSilica）（14）。随后用硫代甲酚处理14将钌络合物去除为（DMPE）2 Ru（H）（SC 6 H 4 Me）（10）。用丙酮处理1得到C-结合的烯酸酯配合物（DMPE）2 Ru（H）（CH 2 C（O）CH 3）（15），产率为34％。末端炔烃与1反应生成钌-乙炔配合物反式-（DMPE）2 Ru（H）（CCPh）16（74％收率）和反式-（DMPE）2
• Alkyl, hydrido and related compounds of ruthenium with trimethylphosphine and bis(1,2-dimethylphosphino)ethane. X-ray crystal structures of cis-hydridoethyltetrakis(trimethylphosphine)-ruthenium(II) and ethylene tetrakis-(trimethylphosphine)ruthenium(0)
  作者：Wai-Kwok Wong、Kwok W. Chiu、John A. Statler、Geoffrey Wilkinson、Majid Montevalli、Michael B. Hursthouse

  DOI：10.1016/s0277-5387(00)84672-0

  日期：1984.1

  ethylene is bound in the η2 or metallocyclopropane form, which is confirmed by a single-crystal X-ray diffraction study. This shows a relatively long carbon-carbon bond distance of 1.44(1)A between the “ethylene” carbons. The structure of cis-Ru(H)(C2H5)(PMe3)4 has also been confirmed by a single-crystal X-ray diffraction study. Possible mechanisms for the observed reactivities are considered.

  摘要根据反应条件和烷基的不同，反式RuCl2（PMe3）4与R2Mg的相互作用给出R =（C2H4）Ru（PMe3）4或顺式Ru（H）（C2H5）（PMe3）4。乙基和顺式Ru（H）（nC3H7（PMe3）4对于R =正丙基。Et2Mg与反式RuX2（dmpe）2（X = Cl，CO2Me）的相互作用产生顺式（Rut（Et2）dmpe对于X = Cl为2）或对于X = CO2Me为反式Ru（Et）2（dmpe）2）。（ ）Ru（PMe3）4的NMR数据表明，乙烯以η2或金属环丙烷的形式结合，这已通过单晶X射线衍射研究得到证实。这表明“乙烯”碳之间的碳-碳键间距离相对较长，为1.44（1）A。单晶X射线衍射研究也证实了顺式Ru（H）（ ）（PMe3）4的结构。考虑观察到的反应性的可能机制。
• Hall, Chris; Jones, William D.; Mawby, Roger J., Journal of the American Chemical Society, 1992, vol. 114, # 19, p. 7425 - 7435
  作者：Hall, Chris、Jones, William D.、Mawby, Roger J.、Osman, Robert、Perutz, Robin N.、Whittlesey, Michael K.

  DOI：——

  日期：——