Просмотр кода страницы Английская Википедия:Dicarbonyltris(triphenylphosphine)ruthenium(0)

{{Английская Википедия/Панель перехода}}
{{chembox
| Name=Dicarbonyltris(triphenylphosphine){{shy}}ruthenium(0)
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 428797226
| ImageFile = 
| ImageSize = 
| ImageFile1 = Roper's-complex-trans-isomer-3D-skeletal-sticks.png
| IUPACName = (''TBPY''-5-22)-dicarbonyltris<br />(triphenylphosphane)ruthenium(0)
| OtherNames = 
|Section1={{Chembox Identifiers
| CASNo_Ref = {{cascite|changed|??}}
| CASNo = 35880-54-7
| ChemSpiderID = 9117254
| PubChem = 10942026
| SMILES = c3c(P(c1ccccc1)c2ccccc2)cccc3.c3c(P(c1ccccc1)c2ccccc2)cccc3.c3c(P(c1ccccc1)c2ccccc2)cccc3.[Ru].[C-]#[O+].[C-]#[O+]
| StdInChI=1S/3C18H15P.2CO.Ru/c3*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;2*1-2;/h3*1-15H;;;
| StdInChIKey=VBLLGXDCYTWKHI-UHFFFAOYSA-N
  }}
|Section2={{Chembox Properties
| C=56 | H=45 | O=2 | P=3 | Ru=1
| MolarMass = 
| Appearance = pale yellow solid
| Density = 
| MeltingPt = 
| BoilingPt = 
| Solubility = insoluble
  }}
|Section3={{Chembox Hazards
| MainHazards = 
| FlashPt = 
| AutoignitionPt = 
  }}
}}
'''Dicarbonyltris(triphenylphosphine)ruthenium(0)''' or '''Roper's complex''' is a [[ruthenium]] [[metal carbonyl]].<ref name=Roper>{{cite journal |author1=B. E. Cavit |author2=K. R. Grundy |author3=W. R. Roper | title = Ru(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> and Os(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub>. An ethylene complex of ruthenium and a dioxygen complex of osmium | year = 1972 | journal = [[Chemical Communications|Journal of the Chemical Society, Chemical Communications]] | issue = 2 | pages = 60–61 | doi = 10.1039/C3972000060b }}</ref> In it, two [[carbon monoxide]] [[ligand]]s and three [[triphenylphosphine]] ligands are coordinated to a central ruthenium(0) center.

In solution, this compound readily dissociates one of the three phosphine ligands, thereby generating a reactive 16-electron complex that binds or oxidatively adds a variety of substrates such as [[alkyne]]s, [[olefin]]s, [[hydrogen|dihydrogen]], and [[oxygen|dioxygen]]. The compound has a [[trigonal bipyramidal molecular geometry]] and, in solution, exists as a mixture of two isomers that rapidly interconvert.  The complex is air stable as a solid, but its solutions oxygenate in air to afford Ru(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>(η<sup>2</sup>-O<sub>2</sub>).

== Preparation ==
The compound can be prepared by [[magnesium]] [[Redox|reduction]] of the corresponding ruthenium(II) dichloride complex in the presence of an excess of phosphine. The 16-electron intermediate can actually be isolated.
:Ru(CO)<sub>2</sub>Cl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> + Mg + PPh<sub>3</sub> → Ru(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> + MgCl<sub>2</sub>

An improved [[base (chemistry)|base]]-promoted method involves the reduction of a ruthenium(II) carbonyl chloride with base in the presence of excess phosphine.<ref>{{cite journal | author = Stephane Sentets, Maria del Carmen Rodriguez Martinez, Laure Vendier, Bruno Donnadieu, Vincent Huc, Noël Lugan, and Guy Lavigne | title = Instant "Base-Promoted" Generation of Roper's-type Ru(0) Complexes Ru(CO)<sub>2</sub>(PR<sub>3</sub>)<sub>3</sub> from a Simple Carbonylchlororuthenium(II) Precursor | year = 2005 | journal = [[Journal of the American Chemical Society|J. Am. Chem. Soc.]] | volume = 127 | issue = 42 | pages = 14554–14555 | doi = 10.1021/ja055066e | pmid = 16231891 }}</ref>  The overall reaction for this [[one-pot synthesis]] is:
:Ru(CO)<sub>3</sub>Cl<sub>2</sub>(thf) + 3 PPh<sub>3</sub>  +  4 [NEt<sub>4</sub>]OH  →  Ru(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>  +  [NEt<sub>4</sub>]<sub>2</sub>[CO<sub>3</sub>] + 2 [NEt<sub>4</sub>]Cl  +  2H<sub>2</sub>O  +  thf
The first step in this sequence is the formation of a metallocarboxylate by nucleophilic attack of [[hydroxide]] anion on a CO ligand to form a [[formic acid|formate]] anion:
:Ru(CO)<sub>3</sub>Cl<sub>2</sub>(thf) + [NEt<sub>4</sub>]OH  →  [NEt<sub>4</sub>][Ru(CO)<sub>2</sub>(COOH)Cl<sub>2</sub>(thf)]

Next solvated [[tetrahydrofuran]] is replaced by phosphine:  
:[NEt<sub>4</sub>][Ru(CO)<sub>2</sub>(COOH)Cl<sub>2</sub>(thf)]  +  PPh<sub>3</sub>  →  [NEt<sub>4</sub>][Ru(CO)<sub>2</sub>(COOH)Cl<sub>2</sub>(PPh<sub>3</sub>)]  +  thf

Next the formate ligand is [[deprotonation|deprotonated]] again by [[hydroxide]]:
:[NEt<sub>4</sub>][Ru(CO)<sub>2</sub>(COOH)Cl<sub>2</sub>(PPh<sub>3</sub>)]  +  [NEt<sub>4</sub>]OH    →  [NEt<sub>4</sub>]<sub>2</sub>[Ru(CO)<sub>2</sub>(COO)Cl<sub>2</sub>(PPh<sub>3</sub>)]  +  H<sub>2</sub>O

These three reactions mean that [[carbon monoxide]] has been oxidized to [[carbon dioxide]] with the concomitant reduction of Ru(II) to Ru(0). Finally, the two remaining chloride ligands are replaced by two more phosphine groups and the carbon dioxide leaves:

:[NEt<sub>4</sub>]<sub>2</sub>[Ru(CO)(COO)Cl<sub>2</sub>(PPh<sub>3</sub>)] +  2 PPh<sub>3</sub>  →  Ru(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub>  + CO<sub>2</sub>  +  2 [NEt<sub>4</sub>]Cl

The generated carbon dioxide is trapped as [[ammonium carbonate|[NEt<sub>4</sub>]<sub>2</sub>[CO<sub>3</sub>]]].

==History==
The complex was first reported by Warren R Roper and his coworkers in 1972 in an era where oxidative addition reactions to ''d''<sup>8</sup> metal complexes were first being systematically examined.<ref name=Roper/> Being zero-valent and carrying only two CO ligands, the complex is highly nucleophilic.  Many of its reactions parallel those for [[Vaska's complex]].

==Applications==
The derivative Ru(CO)<sub>2</sub>H<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>, obtained by exposing the complex to [[hydrogen]], is a [[catalyst]] in the [[Murai olefin coupling]] reaction between terminal [[alkene]]s and the [[aromatic ortho substituent|ortho]] C-H position of a [[phenone]].

== References ==
<references/>
{{Ruthenium compounds}}

[[Category:Ruthenium complexes]]
[[Category:Carbonyl complexes]]
[[Category:Triphenylphosphine complexes]]
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