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{{Ruthenium compounds}}
 
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{{chembox
{{chembox
| Name = Dicarbonyltris(triphenylphosphine){{shy}}ruthenium(0)
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| verifiedrevid = 372075213
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| verifiedrevid = 428797226
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| ImageFile1 = Roper's-complex-trans-isomer-3D-balls.png
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| IUPACName = (''TBPY''-5-22)-dicarbonyltris<br />(triphenylphosphane)ruthenium(0)
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| ImageFile1 = Roper's-complex-trans-isomer-3D-skeletal-sticks.png
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| Section1 = {{Chembox Identifiers
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| IUPACName = (''TBPY''-5-22)-dicarbonyltris<br />(triphenylphosphane)ruthenium(0)
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| Section1 = {{Chembox Identifiers
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| CASNo_Ref = {{cascite|changed|??}}
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| CASNo = 35880-54-7
| ChemSpiderID = 9117254
| PubChem = 10942026
| SMILES = [O+]#C[Ru-5](C#[O+])([P+](c1ccccc1)(c2ccccc2)c3ccccc3)([P+](c1ccccc1)(c2ccccc2)c3ccccc3)[P+](c1ccccc1)(c2ccccc2)c3ccccc3
| 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
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| Section2 = {{Chembox Properties
| Section2 = {{Chembox Properties
| C=56 | H=45 | O=2 | P=3 | Ru=1
| Formula = C<sub>56</sub>H<sub>45</sub>O<sub>2</sub>P<sub>3</sub>Ru
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| Appearance = pale yellow solid
| Appearance = pale yellow solid
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| Solubility = insoluble
| Solubility = insoluble
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| Section3 = {{Chembox Hazards
| Section3 = {{Chembox Hazards
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'''Dicarbonyltris(triphenylphosphine)ruthenium(0)''' or '''Roper's complex''' is a [[ruthenium]] [[metal carbonyl]]<ref name=Roper>{{cite journal | author = B. E. Cavit, K. R. Grundy and 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.
'''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>).
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>).
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: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>
: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:
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
: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:
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:
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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:
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
:[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>]]].
The generated carbon dioxide is trapped as [[ammonium carbonate|[NEt<sub>4</sub>]<sub>2</sub>[CO<sub>3</sub>]]].
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==Applications==
==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]].
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]].

== External links ==
* [http://staff.bath.ac.uk/chsmkw/RUD_2.html Murai reaction]


== References ==
== References ==
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{{Ruthenium compounds}}
{{Ruthenium compounds}}


[[Category:Ruthenium compounds]]
[[Category:Ruthenium complexes]]
[[Category:Carbonyl complexes]]
[[Category:Carbonyl complexes]]
[[Category:Triphenylphosphine complexes]]
[[Category:Ruthenium(0) compounds]]
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