[Ru(CO)₄(PMe₃)] | 97233-17-5

• 英文名称: [Ru(CO)₄(PMe₃)]
• CAS: 97233-17-5；93180-37-1
• 化学式: C₇H₉O₄PRu
• 分子量: 289.19
• InChiKey: FMTZBXWWCGWAGU-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(CO)₄(PMe₃)] 在 碘甲烷 作用下， 以 further solvent(s) 为溶剂， 以49%的产率得到fac-Ru(PMe3)(CO)3(Me)I
  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：

  ruthenium tetracarbonyl 以 Petroleum ether 为溶剂， 生成 [Ru(CO)₃(PMe₃)₂] 、 [Ru(CO)₄(PMe₃)]
  参考文献：
  名称：

  Hastings, W. Ross; Baird, Michael C., Inorganic Chemistry, 1986, vol. 25, # 16, p. 2913 - 2915

  摘要：

  DOI：

文献信息

• Complexes Containing Unbridged Dative Metal−Metal Bonds and the Strong Acceptor Ru(CO)₃(SiCl₃)₂ Moiety. Comments on the Transition Metal to Silicon Bond
  作者：Faming Jiang、Jonathan L. Male、Kumar Biradha、Weng Kee Leong、Roland K. Pomeroy、Michael J. Zaworotko

  DOI：10.1021/om980116s

  日期：1998.12.1

  trans to the metal bond in 1M, whereas the isocyanide ligands are cis to this bond in 3M. The ButNC substituents have a cis configuration in 3Fe and 3Ru, but a trans arrangement in 3Os. Complexes 3Fe, 1Ru, and 3Ru are rare examples of structurally characterized compounds in which a first-row or second-row transition metal acts as the donor atom in a molecule containing an unbridged dative bond between two

  式的复合物（R 3 P）（OC）4 MRU（CO）3硅烷（SiCl 3）2（M =钌，锇）及（OC）3（BU吨NC）2 MRU（CO）3硅烷（SiCl 3）2（M ＝ Fe，Ru，Os）是在室温下由顺式-Ru（CO）4（SiCl 3）2与合适的供体分子反应制得的。配合物的表征包括（Me 3 P）（OC）4 MRu（CO）3（SiCl 3）2的晶体结构（M = RU，1RU ;锇，1Os）和三个M（CO）3（CNBu吨）2个衍生物（3FE，3RU，3Os）。所有这五个结构揭示了具有未桥连的金属-金属键的分子。PMe 3配体在1M中反到金属键，而异氰配体在3M中顺式结合到金属键。卜吨NC取代基具有顺式构型3FE和3RU，但在反式排列3Os。配合3FE，1RU和3RU在结构上具有特征的化合物的稀有例子是，其中第一行或第二行过渡金属在两个过渡金属之间包含未桥键键的分子中充当供体原子。的（OC）3（BU吨NC）2
• Dissociation and isomerization of (OC)5OsRu(CO)3(SiCl3)(Br), a compound with an osmium—ruthenium donor—acceptor bond
  作者：Marcia M. Fleming、Roland K. Pomeroy、Paul Rushman

  DOI：10.1016/0022-328x(84)80536-7

  日期：1984.9

  In solution the donor—acceptor complex (OC)5OsRu(CO)3(SiCl3)(Br) (Ia) partially dissociates to Os(CO)5 and [Ru(CO)3(SiCl3)(Br)]2. On further standing in solution Ia isomerizes to (Br)(OC)4OsRu(CO)4(SiCl3).

  在溶液中，供体-受体配合物（OC）5 OsRu（CO）3（SiCl 3）（Br）（Ia）部分解离为Os（CO）5和[Ru（CO）3（SiCl 3）（Br）] 2。在溶液中进一步静置时，Ia异构化为（Br）（OC）4 OsRu（CO）4（SiCl 3）。
• 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 ]。
• QALE analysis of CO dissociative kinetics of Ru(CO)₄L (L = P-donor ligands): accelerating effects of hydrogen in PH_nR_3 − nligands (n = 1–2)
  作者：Claudia Babij、Lezhan Chen、Igor O. Koshevoy、Anthony J. Poë

  DOI：10.1039/b315719a

  日期：——

  Studies of CO-dissociative substitution reactions of the complexes Ru(CO)4L (L = a wide variety of P-donor ligands) have been extended and analysis of the results by the QALE methodology has been refined (QALE = quantitative analysis of ligand effects). Rates increase substantially with increasing size of L, mainly as a consequence of increasingly favourable activation entropies. These can be associated

  Ru（CO）4配合物的CO-解离取代反应研究L（L =多种P-供体配体）已得到扩展，并且QALE方法对结果的分析也得到了完善（QALE =配体效应的定量分析）。速率随着L大小的增加而显着增加，这主要是由于激活熵越来越有利的结果。这些可能与增加的Ru-CO键断裂有关，该断裂通过增加空间应变释放所允许的增加的Ru-P键进行焓补偿。显着的π酸度允许值显示这些影响是显着的，而σ供体和芳基的影响则可以忽略不计。但是，直接连接到磷原子上的侧链氢原子对速率具有明显而独特的积极影响，并具有显着的动力学同位素效应（KIE）。这与直接Ru–H或初始Ru–（η的新出现有关2 -P–H）随着CO配体的脱离而产生的不良键。