My watch list  

Dicarbonyltris(triphenylphosphine)ruthenium (0)

Dicarbonyltris(triphenylphosphine)ruthenium (0) or Roper's complex is a ruthenium metal carbonyl [1]. In Ru(CO)2(PPh3)3 carbon monoxide ligands and three triphenylphosphine ligands are coordinated to a central ruthenium atom. This compound loses a phosphine ligand very easily can replace it alkynes or olefins. The related organometallic complex Ru(CO)2H2(PPh3)2 can be obtained by exposing the complex to hydrogen gas and is a catalyst in the Murai olefin coupling reaction between terminal alkenes and the ortho C-H position of a phenone.


The compound can be prepared by magnesium reduction in the presence of a large excess of phosphine. The 16-electron intermediate can actually be isolated.

Ru(CO)_2Cl_2(PPh_3)_2 + Mg + PPh_3  \longrightarrow Ru(CO)_2(PPh_3)_2 \longrightarrow Ru(CO)_2(PPh_3)_3

A recent base promoted method involves the reduction of bivalent ruthenium in tricarbonyldichloro ruthenium (II) with triphenylphosphine and the ammonium salt tetraethylammonium hydroxide [2]. The overall reaction for this one-pot synthesis is:

Ru(CO)_3Cl_2(THF) +  3 PPh_3 + 4NEt_4OH  \longrightarrow Ru(CO)_2(PPh_3)_2 + (NEt_4)_2CO_3 + 2 NEt_4Cl + 2 H_2O

but the reactants are added sequentially. The first step is the formation of a hydroxyl - carbonyl adduct to an anion:

Ru(CO)_3Cl_2(THF) + NEt_4OH   \longrightarrow (NEt_4)^+Ru(CO)(COOH)(Cl)_2(THF)^-

next solvatated tetrahydrofuran is replaced by phosphine:

(NEt_4)^+Ru(CO)(COOH)(Cl)_2^-  +  PPh_3  \longrightarrow (NEt_4)^+Ru(CO)(COOH)(Cl)_2PPh_3^-  + THF

next the carboxylic acid ligand is deprotonated by hydroxide forming the dianion and water

(NEt_4)^+Ru(CO)(COOH)(Cl)_2PPh_3^-   +   NEt_4OH    \longrightarrow (NEt_4)_2^+Ru(CO)(COO)(Cl_2)PPh_3^{2-}  + H_2O

in this compound carbon monoxide is effectively oxidized to carbon dioxide with the reduction of Ru (II) to Ru(0) and in a dissociative chemical reaction carbon dioxide is removed. The two remaining chlorine ligands are replaced by two more phosphine groups in the final step.

(NEt_4)_2^+Ru(CO)(COO)(Cl)_2PPh_3^{2-} +   2PPh_3 \longrightarrow Ru(CO)_2(PPh_3)_3  + CO_2 +  2 NEt_4Cl

The generated carbon dioxide is trapped:

CO_2 +   2 NEt_4OH  \longrightarrow (NEt_4)_2CO_3 + H_2O

In this sequence low reaction temperatures and the order in which the reagents are added are important. Ru(CO)2(PPh3)3 is air stable when dry but in THF conversion occurs to Ru(CO)2(PPh3)3O2. The compound has a trigonal bipyramidal molecular geometry and exists as a mixture of two isomers that rapidly interconvert in solution.


  1. Cavit, B. E.; Grundy, K. R.; Roper, W. R. J. Chem. Soc., Chemical Communications. 1972, 60.
  2. Instant "Base-Promoted" Generation of Roper's-type Ru(0) Complexes Ru(CO)2(PR3)3 from a Simple Carbonylchlororuthenium(II) Precursor Stephane Sentets, Maria del Carmen Rodriguez Martinez, Laure Vendier, Bruno Donnadieu, Vincent Huc, Noël Lugan, and Guy Lavigne J. Am. Chem. Soc.; 2005; 127(42) pp 14554 - 14555; (Communication) DOI: 10.1021/ja055066e Abstract
This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Dicarbonyltris(triphenylphosphine)ruthenium_(0)". A list of authors is available in Wikipedia.
Your browser is not current. Microsoft Internet Explorer 6.0 does not support some functions on Chemie.DE