[Ru(CO)₃(PMe₃)₂] | 75687-45-5

• 英文名称: [Ru(CO)₃(PMe₃)₂]
• 英文别名: Ru(CO)₃(PMe₃)₂
• CAS: 75687-45-5
• 化学式: C₉H₁₈O₃P₂Ru
• 分子量: 337.258
• InChiKey: JVKTZHNAMOOFDP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 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(CO)₃(PMe₃)₂] 在 碘甲烷 作用下， 以 further solvent(s) 为溶剂， 以79%的产率得到cis-RuMeI(CO)2(PMe3)2
  参考文献：
  名称：

  Oxidative addition of methyl iodide to monosubstituted and disubstituted derivatives of ruthenium pentacarbonyl: preparation of neutral and ionic complexes of ruthenium

  摘要：

  The oxidative addition of CH3I to Ru(CO)4PMe3 (1) gives the methyl complex Ru(CO)3PMe3(CH3)I (3); with PMe3 complex 3 gives the acetyl complexes Ru(CO)2(PMe3)2(COCH3)I (isomers 10a and 10b), which, by decarbonylation, give Ru(CO)2(PMe3)2(CH3)I (4). Complex 4 can also be obtained by oxidative addition of CH3I to Ru(CO)3(PMe3)2 (2). Complex 4 reacts at room temperature with the nucleophiles CO, PMe3, and P(OMe)3 giving the acetyl complexes (structures 7, 15, and 18, respectively), which at higher temperatures isomerize to 8, 16, and 19, respectively. Decarbonylation of these complexes gives complex 4 (in the case of CO), complex 12 (in the case of PMe3), and complex 13 (in the case of P(OMe)3). This last complex reacts with different nucleophiles (PMe3, P(OMe)3) and gives the ionic tetraphosphine complexes [Ru(CO)(PMe3)3P(OMe)3(CH3)]I (22) and [Ru(CO)(PMe3)2(P(OMe)3)2(CH3)]BPh4 (24), respectively. The trisubstituted cyano derivative Ru(CO)(PMe3)2P-(OMe)3(CH3)CN (14) is obtained by the reaction of complex 22 with KCN in acetone. The structures of the various complexes were assigned, in most cases, on the basis of spectroscopic (IR, H-1, P-31, C-13) information.

  DOI：

  10.1021/ic00057a011
• 作为产物：
  描述：

  cis-[Ru(PMe3)4(H)(NHC6H5)] 在 CO 作用下， 以 氘代苯 为溶剂， 以79%的产率得到[Ru(CO)₃(PMe₃)₂]
  参考文献：
  名称：

  Hartwig, John F.; Andersen, Richard A.; Bergman, Robert G., Organometallics, 1991, vol. 10, # 6, p. 1875 - 1887

  摘要：

  DOI：

文献信息

• Further chemistry of tris(µ-methylene)-hexakis(trimethylphosphine)diruthenium(<scp>III</scp>). Synthesis and X-ray crystal structures of bis[bis(µ-methylene)-tetrakis(trimethylphosphine)ruthenium(<scp>III</scp>)]ruthenium(<scp>IV</scp>)-(Ru–Ru–Ru) bis(tetrafluoroborate), tris(µ-hydroxo)-hexakis(trimethylphosphine)diruthenium(<scp>II</scp>) tetrafluoroborate, and tricarbonylbis(trimethylphosphine)ruthenium(<scp>0</scp>)
  作者：Richard A. Jones、Geoffrey Wilkinson、Anita M. R. Galas、Michael B. Hursthouse、K. M. Abdul Malik

  DOI：10.1039/dt9800001771

  日期：——

  Further chemistry of the triple methylene (–CH2–) bridged compound Ru2(µ-CH2)3(PMe3)6 and its derivatives is described. The compounds [(Me3P)4Ru(µ-CH2)2Ru(µ-CH2)2Ru(PMe3)4][BF4]2, (1), and [Ru2(µ-OH)3(PMe3)6][BF4], (2), have been isolated from the interaction of aqueous fluoroboric acid with a red oil obtained during the synthesis of Ru2(µ-CH2)3(PMe3)6. Interaction of carbon monoxide (5 atm) with Ru2(µ-CH2)3(PMe3)6

  描述了三亚甲基（–CH 2 –）桥接化合物Ru 2（µ-CH 2）3（PMe 3）6及其衍生物的进一步化学反应。化合物[（Me 3 P）4 Ru（µ-CH 2）2 Ru（µ-CH 2）2 Ru（PMe 3）4 ] [BF 4 ] 2，（1）和[Ru 2（µ-OH） ）3（PMe 3）6 ] [BF 4]，（2）已从氟硼酸水溶液与Ru 2（µ-CH 2）3（PMe 3）6的合成过程中获得的红色油的相互作用中分离出来。一氧化碳（5 atm）与Ru 2（µ-CH 2）3（PMe 3）6相互作用，得到反式-Ru（PMe 3）2（CO）3，（3）。已通过红外和核磁共振（1 H和31 P）光谱研究了这些化合物，并确定了它们的X射线结构。
• Ruthenium Dihydride Complexes:  NMR Studies of Intramolecular Isomerization and Fluxionality Including the Detection of Minor Isomers by Parahydrogen-Induced Polarization
  作者：Daniele Schott、Christopher J. Sleigh、John P. Lowe、Simon B. Duckett、Roger J. Mawby、Martin G. Partridge

  DOI：10.1021/ic011255w

  日期：2002.6.1

  studies reveal that complexes Ru(CO)(2)(H)(2)L(2) (L = PMe(3), PMe(2)Ph, and AsMe(2)Ph) can have three geometries, ccc, cct-L, and cct-CO, with equilibrium ratios that are highly dependent on the electronic properties of L; the cct-L form is favored, because the sigma-only hydride donor is located trans to CO rather than L. When L = PMe(3), the ccc form is only visible when p-H(2) is used to amplify its

  NMR研究显示，配合物Ru（CO）（2）（H）（2）L（2）（L = PMe（3），PMe（2）Ph和AsMe（2）Ph）可以具有三种几何形状，ccc， cct-L和cct-CO，其平衡比高度依赖于L的电子性质；cct-L形式是受青睐的，因为只有sigma的氢化物供体位于CO而非L处。当L = PMe（3）时，仅当使用pH（2）放大其光谱特征时ccc形式才可见。相反，当L = AsMe（2）Ph时，ccc和cct-L形式的含量相似，因此必须具有相似的自由能。但是，对于这种配合物，cct-CO异构体也是可检测的。这些复合体经历了许多动态过程。对于L（2）= dppe，ccc形式中氢化物位置的互换显示出伴随同步的CO交换和两个磷原子的互换。认为该过程涉及包含eta（2）-H（2）配体的三角双锥体过渡态的形成。鉴于k（HH）/ k（DD）为1.04且L（2）= dppe时同步旋转，该过渡状态必须
• A combined parahydrogen and theoretical study of H2 activation by 16-electron d8 ruthenium(0) complexes and their subsequent catalytic behaviour
  作者：John P. Dunne、Damir Blazina、Stuart Aiken、Hilary A. Carteret、Simon B. Duckett、Jonathan. A. Jones、Rinaldo Poli、Adrian C. Whitwood

  DOI：10.1039/b410912k

  日期：——

  The photochemical reaction of Ru(CO)3(L)2, where L = PPh3, PMe3, PCy3 and P(p-tolyl)3 with parahydrogen (p-H2) has been studied by in-situ NMR spectroscopy and shown to result in two competing processes. The first of these involves loss of CO and results in the formation of the cis-cis-trans-L isomer of Ru(CO)2(L)2(H)2, while in the second, a single photon induces loss of both CO and L and leads to the formation of cis-cis-cis Ru(CO)2(L)2(H)2 and Ru(CO)2(L)(solvent)(H)2 where solvent = toluene, THF and pyridine (py). In the case of L = PPh3, cis-cis-trans-L Ru(CO)2(L)2(H)2 is shown to be an effective hydrogenation catalyst with rate limiting phosphine dissociation proceeding at a rate of 2.2 s−1 in pyridine at 355 K. Theoretical calculations and experimental observations show that H2 addition to the Ru(CO)2(L)2 proceeds to form cis-cis-trans-L Ru(CO)2(L)2(H)2 as the major product via addition over the π-accepting OC–Ru–CO axis.

  我们通过原位核磁共振光谱研究了 Ru(CO)3(L)2（其中 L = PPh3、PMe3、PCy3 和 P(对甲苯基)3）与对氢（p-H2）的光化学反应，结果表明该反应有两个相互竞争的过程。第一个过程涉及 CO 的损失，并形成 Ru(CO)2(L)2(H)2 的顺式-顺式-反式-L 异构体，而在第二个过程中，单个光子导致 CO 和 L 的损失，并形成顺式-顺式-Ru(CO)2(L)2(H)2 和 Ru(CO)2(L)(溶剂)(H)2，其中溶剂=甲苯、四氢呋喃和吡啶 (py)。在 L = PPh3 的情况下，顺式-顺式-反式-L Ru(CO)2(L)2(H)2 被证明是一种有效的氢化催化剂，在 355 K 的吡啶中，膦解离的速率限制为 2.2 s-1。理论计算和实验观察结果表明，向 Ru(CO)2(L)2加入 H2 后，通过在接受 π 的 OC-Ru-CO 轴上的加成，形成顺式-顺式-反式-L Ru(CO)2(L)2(H)2，作为主要产物。
• Lewis Acid Binding and Transfer as a Versatile Experimental Gauge of the Lewis Basicity of Fe ⁰ , Ru ⁰ , and Pt ⁰ Complexes
  作者：Holger Braunschweig、Carina Brunecker、Rian D. Dewhurst、Christoph Schneider、Benedikt Wennemann

  DOI：10.1002/chem.201503536

  日期：2015.12.21

  number of zerovalent ruthenium tri‐ and tetracarbonyl complexes of the form [Ru(CO)5−nLn] (n=1, 2) with neutral phosphine or N‐heterocyclic carbene donor ligands have been treated with the Lewis acids GaCl3 and Ag+ to form a range of metal‐only Lewis pairs (MOLPs). The spectroscopic and structural parameters of the adducts are compared to each other and to related iron carbonyl based MOLPs. The Lewis basicity

  许多路易斯酸GaCl 3处理了[Ru（CO）5− n L n ]（n = 1，2）与中性膦或N-杂环卡宾供体配体的零价钌三和四羰基配合物和Ag +形成一系列仅含金属的路易斯对（MOLP）。将加合物的光谱和结构参数相互比较，并与相关的羰基铁基MOLPs进行比较。原钌的路易斯碱度0络合物被转移实验衡量，以及通过结合的GaCl的pyramidization度3单元和钌M键长度。这项工作显示了MOLP概念的好处，它是少数几个直接测试金属碱度的指标，并且可以比较具有不同金属中心和配位体的金属配合物。
• Preparation of Ru(CO)3(PMe3)MeI and its acetyl derivatives
  作者：Giuseppe Cardaci

  DOI：10.1016/0022-328x(87)87137-1

  日期：1987.4

  [Ru(CO)4PMe3] reacts with MeI to give fac-[Ru(CO)3(PMe3)(Me)I]. The latter reacts with PMe3 to give a mixture of the three isomers of cis-bis(trimethylphosphine)-cis-dicarbonyl acetyl iodide [Ru(CO)2(PMe3)2(COMe)I]. Decarbonylation of the mixture gives only the trans-bis(trimethylphosphine)-cis-dicarbonyl methyl iodide complex [Ru(CO)2(PMe3)2MeI], which was also prepared by oxidative addition of MeI

  [Ru（CO）4 PMe 3 ]与MeI反应生成fac- [Ru（CO）3（PMe 3）（Me）I]。后者与PMe 3反应，得到顺式-双（三甲基膦）-顺式-二羰基乙酰碘[Ru（CO）2（PMe 3）2（COMe）I]的三种异构体的混合物。混合物的脱羰基化仅产生反式-双（三甲基膦）-顺式-二羰基甲基碘配合物[Ru（CO）2（PMe 3）2 MeI]，该配合物也可通过将MeI氧化添加至[Ru（CO）3来制备（PMe 3）2 ]。