| Revision as of 18:36, 12 May 2011 editLamro (talk | contribs)Autopatrolled, Extended confirmed users84,339 edits {{Ruthenium compounds}}← Previous edit |
Latest revision as of 14:29, 3 July 2024 edit undoJWBE (talk | contribs)Extended confirmed users10,129 edits added Category:Ruthenium(0) compounds using HotCat |
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| Name = Dicarbonyltris(triphenylphosphine){{shy}}ruthenium(0) |
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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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| Section1 = {{Chembox Identifiers |
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| IUPACName = (''TBPY''-5-22)-dicarbonyltris<br />(triphenylphosphane)ruthenium(0) |
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| CASNo = 35880-54-7 |
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| ChemSpiderID = 9117254 |
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| PubChem = 10942026 |
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| SMILES = #C(C#)((c1ccccc1)(c2ccccc2)c3ccccc3)((c1ccccc1)(c2ccccc2)c3ccccc3)(c1ccccc1)(c2ccccc2)c3ccccc3 |
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| 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;;; |
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| StdInChIKey=VBLLGXDCYTWKHI-UHFFFAOYSA-N |
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| C=56 | H=45 | O=2 | P=3 | Ru=1 |
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| 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 |
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| Appearance = pale yellow solid |
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| Solubility = insoluble |
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| Solubility = insoluble |
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'''Dicarbonyltris(triphenylphosphine)ruthenium(0)''' or '''Roper's complex''' is a ] ]<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 = ] | issue = 2 | pages = 60–61 | doi = 10.1039/C3972000060b }}</ref>. In it, two ] ]s and three ] ligands are coordinated to a central ruthenium(0) center. |
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'''Dicarbonyltris(triphenylphosphine)ruthenium(0)''' or '''Roper's complex''' is a ] ].<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 = ] | issue = 2 | pages = 60–61 | doi = 10.1039/C3972000060b }}</ref> In it, two ] ]s and three ] ligands are coordinated to a central ruthenium(0) center. |
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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 ]s, ]s, ], and ]. The compound has a ] 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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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 ]s, ]s, ], and ]. The compound has a ] 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> |
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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> |
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An improved ]-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 = ] | volume = 127 | issue = 42 | pages = 14554–14555 | doi = 10.1021/ja055066e | pmid = 16231891 }}</ref>. The overall reaction for this ] is: |
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An improved ]-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 = ] | volume = 127 | issue = 42 | pages = 14554–14555 | doi = 10.1021/ja055066e | pmid = 16231891 }}</ref> The overall reaction for this ] is: |
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:Ru(CO)<sub>3</sub>Cl<sub>2</sub>(thf) + 3 PPh<sub>3</sub> + 4 OH → Ru(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> + <sub>2</sub> + 2 Cl + 2H<sub>2</sub>O + thf |
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:Ru(CO)<sub>3</sub>Cl<sub>2</sub>(thf) + 3 PPh<sub>3</sub> + 4 OH → Ru(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> + <sub>2</sub> + 2 Cl + 2H<sub>2</sub>O + thf |
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The first step in this sequence is the formation of a metallocarboxylate by nucleophilic attack of ] anion on a CO ligand to form a ] anion: |
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The first step in this sequence is the formation of a metallocarboxylate by nucleophilic attack of ] anion on a CO ligand to form a ] anion: |
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These three reactions mean that ] has been oxidized to ] 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: |
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These three reactions mean that ] has been oxidized to ] 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: |
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:<sub>2</sub>] + 2 PPh<sub>3</sub> → Ru(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> + CO<sub>2</sub> + 2 Cl |
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:<sub>2</sub> + 2 PPh<sub>3</sub> → Ru(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> + CO<sub>2</sub> + 2 Cl |
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The generated carbon dioxide is trapped as <sub>2</sub>]]. |
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The generated carbon dioxide is trapped as <sub>2</sub>]]. |
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==Applications== |
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==Applications== |
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The derivative Ru(CO)<sub>2</sub>H<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>, obtained by exposing the complex to ], is a ] in the ] reaction between terminal ]s and the ] C-H position of a ]. |
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The derivative Ru(CO)<sub>2</sub>H<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>, obtained by exposing the complex to ], is a ] in the ] reaction between terminal ]s and the ] C-H position of a ]. |
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== External links == |
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== References == |
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== References == |
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{{Ruthenium compounds}} |
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{{Ruthenium compounds}} |
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