Synthesis and Base Hydrolysis of

Cobalt(III) Complex coordinated

by Thioether Ligand

Special Topic lifted from Journal of Chemical Education (2008) Vol. 85
No. 11 pages 1562-1564

Chem 120.1 – 2L

Paul Lloydson J. Alvarez

Froila Marie G. Deniega
Jonathan Paz
Introduction

Cobalt Complexes

 undergo ligand exchange or substitutions slowly as
compared to many other transition metal compounds

 Their slow reactions have made them suitable for

kinetic investigations of their reaction mechanisms.
Cobalt Complexes

 The [Co(en)2(NH2CH2CH2SCH3)]3+ complex

theoretically follows an SN1 pathway in which a

bond cleavage was present initially as well as the
vacancy in the first sphere
 3+ 2+
CH3
NH NH
H2N S OH-
H2N OH CH3
Co Co S
H2N N H2N H2N (1)
NH2 H2 NH2

2+ 2+
NH3 NH3
H3N H3N
Cl K Cl
Co + OH- Co
H3N NH3 H3N NH3
NH3 NH3
(2)
2+ 2+
NH3 NH3
H3 N H3N
Cl Loss of leaving group
Co Co NH2
H3 N NH3 K H3N
NH3 NH3 (3)
5- coordinate complex
2+ 2+
NH3 NH3
H3N H3N
+ H2O OH
Co NH2 Co
H3N FAST H3N NH3
NH3 NH3
(4)
Chemical Kinetics

 Defined as the study of reaction rates, which may be
measured and interpreted.

 May depend on variables such as: pressure,

temperature, and the presence of a catalyst

 The rate of reaction is often found to be proportional to

the concentrations of the reactants raised to a power.
Chemical Kinetics

The rate of reaction is often found to be proportional
to the concentrations of the reactants raised to a
power. For example two reactants A and B, and it
follows that

v = k[A]a[B]b
Chemical Kinetics

 The power to which the concentration of a species is
raised in a rate law is the order of the reaction with
respect to that species. A reaction with the rate law as
in equation above is first-order in A and first-order in B.
 Methods of determining rate order

1) the method of initial rates- the instantaneous rate is
determined just after the reaction begins
2) the integrated rate law, - the rate law are expressed as
differential equations
3) the method of half-lives, where it is determined how
the half life of a reaction depends on the initial
concentration
 UV- Visible spectroscopy

 The absorption of an appropriate quantum of energy
may result in the movement of an electron from one
orbital to another and hence alter the electronic
state of a system.
UV- Visible spectroscopy

 The use of ultraviolet-visible (UV-Vis) spectroscopy in
inorganic chemistry involves electronic transitions in
metal complexes. A characteristic of many d-block
metal complexes is their colors, which arise because
they absorb light in the visible region.
 

Figure 2. schematic representation of a UV- Vis

spectrophotometer.
Objectives

The objectives of this proposed exercise are as follows:
1. To synthesize cobalt (III) thioether complex;

2. To monitor the kinetics of reaction through UV-Visible

spectroscopy; and

3. To determine the experimental rate and rate constant for the

given base hydrolysis reaction.
Experimental Procedure

Synthesis of the intermediate

[Co(H2O)]Cl2 + Distilled water

Dissolved solids

+ 15% diethylamine solution

Stand for 10 minute

Cool in ice bath

+ (NH2CH2CH2S)2

Stir and stand in ice bath

+ KI

Heat to remove water

filtration

** filtrate--Discard to metal container

**residue--intermediate product, [Co(en)2(NH2CH2CH2S)]I2
Synthesis of the thioether ligand

Intermediate product, [Co(en)2(NH2CH2CH2S)]I2

+ CH3I/DMF

Dissolve solids and

Stir and stand for several minutes

+ KI
Stand in ice bath

filtration

Filtrate- discard to heavy metals

container

Residue- Thioether complex

[Co(en)2(NH2CH2CH2SCH3)]I3

Washing of residue to remove

impurities
Kinetics and Characterization of complexes


 The complexes synthesized are subjected to and
characterized by UV-Vis spectroscopy at 282 nm. The
kinetics of the complex is observed using different
concentrations of NaOH (0.100, 0.075, 0.05, 0.025 M)
and subjecting each run to the UV-Vis spectroscopy.
Chemical Hazards

 1,2-Diaminoethane

- corrosive
 iodomethane

- is suspected carcinogen
 diethyl ether

- flammable
 DMF (Dimethylformamide)

- irritant, toxic to the liver and flammabe

Chemical hazards
 Cobalt(II) chloride

- irritant and toxic
 cystamine dihydrochloride

- hazardous in case of ingestion

 all of these chemicals are volatile

 1,2-diaminoethane and iodomethane should be weighed in a fume
hood and transported in close containers to the reaction hood.
Results and Discussion

 Results and Discussion

Synthesis of [Co(en)2(SCH2CH2NH2)]I2

 CoCl2

- source of Co2+

- its dissolution in water resulted to the

formation of a complex in which six aqua ligands are

coordinated to Co2+

CoCl2 + 6H2O  [Co(H2O)6]2+ + 2Cl-

 Ethylenediamine solution

- source of ethylenediamine ligands

Co2+ complex – labile (undergo fast reactions)

 substitution of H2O ligands by en ligands became

favorable
 the stronger field ethylenediamine ligands
displaced four water molecules from [Co(H2O)6]2+

forming [Co(en)2 (H2O)2]2+.

[Co(H2O)6]2+ + 2en  [Co(en)2(H2O)2]2+ + 4H2O

 (NH2CH2CH2S)2

- oxidized Co2+ to Co3+

 Air is excluded from the reaction solutions to

ensure that the disulfide is responsible for the
oxidation of Co(II) to Co(III).
 The reduction of the disulfide to the thiolate
results in the bidentate thiolato ligand being
trapped in the coordinaton sphere of the inert
Co(III) ion.
[Co(en)2(H2O)2]2+ + NH2CH2CH2S - [Co(en)2(SCH2CH2NH2)]2+ + 2H2O
 Co2+ was coupled first with ethylenediamine prior

to oxidation.
 Ethylenediamine is a strong field ligand and the
presence of a strong field ligand enhances the
stability of the Co3+, thus favoring the oxidation of
the Co2+.
 Crystal Field Stabilization Energy (CFSE)

 The negative value of ΔCFSE (-6Dq) shows the

stability of the Co3+ ion over Co2+ in aqueous

medium and also the formation of a more stable
coordinate complex.
 The oxidation of Co2+ is more preferred if it is
coordinated with a stronger field ligand like
ethylenediamine in [Co(en)2(H2O)2]2+ rather than

with a weaker field ligand like water in [Co(H2O)6]2+.

 Potassium iodide

- source of I- counter ions

 The complex was precipitated out as an iodide salt
because iodine, when coupled with cations with
large size, tends to have an extra stabilization for
the complex due to soft acid-soft base interaction
according to the Hard/Soft Acid Base Principle.
[Co(en)2(SCH2CH2NH2)]2+ + 2KI  [Co(en)2(SCH2CH2NH2)]I2 + 2K+
 Synthesis of the Thioether Complex

 The synthesized [Co(en)2(SCH2CH2NH2)]2+ was reacted with
iodomethane in DMF.
 Iodomethane served as an alkylating agent for the complex. The
reaction is an example of an SN2 reaction.
Characterization of the Complexes
 Electronic transition in complexes
 Two types of CT transition

 Ligand to metal charge transfer (LMCT)

transition
 Metal to ligand charge transfer (MLCT)
transition
 Ligand to metal charge transfer transitions

- observed in the spectrum when the metal is in a

high oxidation state
- the ligands contain non-bonding electrons
- involves the transition from an orbital of high
ligand character to an orbital of high metal
character
- ligands involved are of π donor type
- chromate ion, permanganate ion, complexes
with O2-, Cl-, Br-, I-, S2- ligands
 Both complexes exhibit an intense ligand-to-metal
charge transfer (LMCT) transition at 282 nm and a
d-d transition in the visible region.

 The intense LMCT observed in the spectrum of the

complexes is due to the Co(III) and S bond.

 To confirm the presence of a Co(III) – S bond and

that the reactions have gone to completion, the

peak positions and ratios (AUV/AVIS) were compared
to the literature values.

 The calculated peak ratio of A282/A484 was 46 which

compares favorably to the literature value of 47.
Kinetics of the Base Hydrolysis of the Thioether Complex
 UV-Vis spectroscopy was used to study the base
hydrolysis of a cobalt(III) complex coordinated by
thioether ligand.
 In strongly basic solution, the Co-S bond in the

thioether complex breaks as shown by the following

reaction.
 The thioether complex exhibits an intense ligand-
to-metal charge transfer (LMCT) transition at
282 nm due to the Co(III)-S bond.

 This was utilized to monitor the kinetics of the

Co-S cleavage since a loss in absorbance would
occur as the Co-S cleavage occurs.

 Repetitive scans from 350 nm to 250 nm of the

thioether complex in 0.050M NaOH were done to
illustrate the absorbance change that accompanies
the reaction.
 A drop of thioether complex was added to the
thermostatted solution of 0.050M NaOH.

 The mixture was mixed and the absorbance of the

solution was measured at 282 nm at different time
intervals.

 The typical absorbance change observed during

the course of the reaction is shown in the
following figure.
 Several runs were performed using different
concentrations of NaOH until an infinite time
absorbance (Ainf) reading is reached.

 Then, plots of lnIAt – AinfI versus time were

prepared for each base concentration.

Plot of lnIAt – AinfI versus time of 0.050 M NaOH.

 The linearity of the plot showed that the decay of
the thioether complex is a pseudo-first order
reaction.

 The slope of the plots of lnIAt – AinfI versus time

gave the values of the observed rate – order
constant (kobs) at each base concentration.
 Plotting (kobs) and the concentration of –OH
determines the rate of reaction with respect to
[-OH].
 The linearity of this plot suggests that the reaction
is also first order with respect to [-OH].

 The slope of the plot, on the other hand, gave the

second-order rate constant for the reaction.
 The rate expression for the hydrolysis of the
complex can be written as kobs = kK[-OH] based on
the SN1 CB mechanism shown earlier.

 The second order- rate constant (k-OH) that

students obtained from their linear plot of
kobsversus [-OH] is a composite value, kK.
Summary and Conclusion

 The experiment provided another example that
deals with the concept of lability and inertness of the
2+ and 3+ oxidation state of cobalt.
 The preparation of thiolato complex by the oxidizing
ability of disulfides happened through SN2 reaction.
Summary and Conclusion

 The kinetics part of the experiment allowed the
determination of the rate reaction order of the base
hydrolysis in which results from UV-Vis spectrometry
characterized the reaction to be a pseudo-first order.

 the reaction (base hydrolysis) followed an SN1 CB

base hydrolysis mechanism.
 Sala
ma t
pak s a
i ki n
i g…
References

 Atkins, P. and J. de Paula. 2006. Atkins’ Physical
Chemistry. 8th ed. NY: Oxford University Press.

 Bowser, J. R. 1993. Inorganic Chemistry. Pacific Grove,

California: Brooks/Cole Publishing Company.
 
 Houscroft, C. E. and Sharpe, A. G. 2005.An
Introduction to Inorganic Chemistry. United Kingdom:
Pearson Education Limited.