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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

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Melting point 215 °C (decomp.)

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 Structure
Coordination
square planar
geometry
Crystal structure ?
Dipole moment ?D
Hazards
MSDS External MSDS
Main hazards none
NFPA 704
R: none
R/S statement
S: 22-24/25
RTECS number ?
Supplementary data page
Structure and
n, εr, etc.
properties
Thermodynamic Phase behaviour
data Solid, liquid, gas
Spectral data UV, IR, NMR, MS
Related compounds
Other anions IrI(CO)[P(C6H5)3]2
Other cations RhCl(CO)[P(C6H5)3]2
Related compounds Pd[P(C6H5)3]4
Except where noted otherwise, data are given for
materials in their standard state (at 25 °C, 100 kPa)
Infobox disclaimer and references

Vaska's complex is the trivial name for trans-chlorocarbonylbis(triphenylphosphine)-

iridium(I) with the formula IrCl(CO)[P(C6H5)3]2. This square planar diamagnetic
organometallic complex consists of a central iridium atom bound to two mutually trans
triphenylphosphine ligands as well as carbon monoxide, and chloride. The complex was
reported by Di Luzio and Vaska in 19611. Vaska's complex can undergo oxidative
additions and is notable for its ability to bind to O2 reversibly. It is a bright yellow
crystalline solid.

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Preparation

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.

H2IrCl6 + 3.5P(C6H5)3 + HCON(CH3)2 + 4C6H5NH2 + 1.5H2O → IrCl(CO)

[P(C6H5)3]2 + (CH3)2NH2+Cl- + 1.5 OP(C6H5)3

Typical sources of iridium used in this preparation are IrCl3.xH2O and H2IrCl6.

Reactions

Studies on Vaska's complex provided a conceptual framework for homogeneous catalysis.

Vaska's complex, with 16 valence electrons, is considered "unsaturated" and can thus
bind to one two-electron or two one-electron ligands to become electronically saturated
with 18 valence electrons. The addition of two one-electron ligands is called oxidative
addition. Upon oxidative addition, the oxidation state of the iridium increases from Ir(I)
to Ir(III). The four-coordinated square planar arrangement in the starting complex
converts to an octahedral, six-coordinate product. Vaska's complex undergoes oxidative
addition with conventional oxidants such as halogens, strong acids such as HCl, and other
molecules known to react as electrophiles, such as iodomethane (CH3I).

An interesting characteristic of Vaska's complex is that it binds O2 reversibly.

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.

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Spectroscopy

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.

 Vaska's Complex: 1967 cm-1

 Vaska's + O2: 2015 cm-1
 Vaska's + MeI: 2047 cm-1
 Vaska's + I2: 2067 cm-1

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

 Note 1: L. Vaska and J.W. DiLuzio "Carbonyl and Hydrido-Carbonyl Complexes

of Iridium by Reaction with Alcohols. Hydrido Complexes by Reaction with
Acid" J. Am. Chem. Soc., 83, 2784-5 (1961).DOI: 10.1021/ja01473a054
 Note 2: Girolami, G.S.; Rauchfuss, T.B.; Angelici, R.J. Synthesis and Technique
in Inorganic Chemistry, Third ed.; University Science Books.: Sausalito, 1999,
pp190.
 Note 3: L. Vaska and J.W. DiLuzio J. Am. Chem. Soc., 84, 679 (1962).
 Note 4: Crabtree, R. The Organometallic Chemistry of the Transition Metals;
Third Ed.; John Wiley & Sons, Inc.: Canada, 2001, pp152.

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