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Handout1 Vaska Compound
Handout1 Vaska Compound
Vaska's complex
From Wikipedia, the free encyclopedia.
Vaska's complex
General
Systematic name Carbonychlorolbis(triphenylphosphine)iridium(I)
Iridium(I)bis(triphenylphosphine)
carbonyl chloride
Other names
Vaska's complex
Vaska's compound
Molecular formula IrCl(CO)[P(C6H5)3]2.
Molar mass 780.25 g/mol
Appearance yellow crystals
CAS number [14871-41-1]
EINECS number 238-941-6
Properties
Density and phase ? g/cm3, ?
Solubility in water insol
Other solvents sparingly: benzene
The synthesis involves heating virtually any iridium chloride salt with P(C6H5)3 with a
CO source. The most popular method uses dimethylformamide (DMF) as a solvent.
Sometimes aniline is added to accelerate the reaction. Another popular solvent is 2-
methoxyethanol. The reaction typically is conducted under nitrogen. In the synthesis,
triphenylphosphine serves as both a ligand and a reductant, and the carbonyl ligand is
derived by decomposition of dimethylformamide probably via a deinsertion of an
intermediate Ir-C(O)H species. The following is a possible balanced equation for this
complicated reaction2.
Typical sources of iridium used in this preparation are IrCl3.xH2O and H2IrCl6.
Reactions
IrCl(CO)[P(C6H5)3]2 + O2 ↔ IrCl(CO)[P(C6H5)3]2O2
The dioxygen ligand is bonded to Ir(I) via both oxygen atoms, so-called side-on bonding.
In myoglobin and hemoglobin, O2 binds "end-on," attaching to the metal via only one of
the two oxygen atoms. The oxygenation reaction is carried out simply by bubbling O2
through a solution of Vaska's complex in toluene, which results in a colour change from
yellow to orange. The resulting dioxgen adduct reverts to the parent complex upon
heating in boiling benzene solution.
Infrared spectroscopy can be used to analyse the products of oxidative addition to Vaska's
complex because the reactions induce characteristic shifts of the stretching frequency of
the coordinated carbon monoxide.{fn|3}}. These shifts are dependent on the amount of π-
back bonding allowed from the newly associated ligands. The CO stretching frequencies
for Vaska's complex and oxidatively added ligands have been documented in literature4.
Oxidative addition to give Ir(III) products reduces the π-bonding from Ir to C, which
causes the increase in the frequency of the carbonyl stretching band. The stretching
frequency changes depending on the ligands that have been added, but is always greater
than 2000 cm-1 for an Ir(III) complex.
References