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Vaska's complex
From Wikipedia, the free encyclopedia.
Vaska's complex
General
Systematic name
Carbonychlorolbis(triphenylphosphine)iridium(I)
Other names
Iridium(I)bis(triphenylphosphine)
carbonyl chloride
Vaska's complex
Vaska's compound
780.25 g/mol
Appearance
yellow crystals
CAS number
[14871-41-1]
EINECS number
238-941-6
Properties
sparingly: benzene
Melting point
215 C (decomp.)
Structure
Coordination
geometry
square planar
Crystal structure
Dipole moment
?D
Hazards
MSDS
External MSDS
Main hazards
none
NFPA 704
R/S statement
R: none
S: 22-24/25
RTECS number
n, r, etc.
Thermodynamic
data
Phase behaviour
Solid, liquid, gas
Spectral data
Other anions
IrI(CO)[P(C6H5)3]2
Other cations
RhCl(CO)[P(C6H5)3]2
Related compounds
Pd[P(C6H5)3]4
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 2methoxyethanol. 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.
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 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 -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