Inorganic-Chemical Practical Course

Spring Semester 2014

tris(ethylenediamine)cobalt(III) chloride
([Co(en)3]Cl3)
H2
H2
N H2 N
N
Cl3

Co
N N
H2 H2

N
H2

and
[Co(dinosar)]Br3
NO2
HN

NH

HN

Br 3

Co
HN

NH

NH

NO2

27/05/2014
Patrick Zwick
B2

Patrick Zwick

Exp 5

1 Aim of the experiment

The aim of the experiment was the synthesis of tris(ethylenediamine)cobalt(III) chloride
([Co(en)3]Cl3)

as

well

as

the

synthesis

of

1,8-dinitro-3,6,10,13,16-

hexaazabicyclo[6,6,6]eicosane cobalt(III) bromide ([Co(dinosar)]Br3). The cryptand ligand

dinosar was built around the metal centre of tris(ethylenediamine)cobalt(III) using template
methodology. The product [Co(en)3]Cl3 was analysed by 1H-NMR spectroscopy in two
different solvents (D2O and DMSO-d6). The product [Co(dinosar)]Br3 was analysed by 1HNMR spectroscopy in comparison with the spectra given by the instruction[2].

2 Introduction
The synthesized products are Co(III) complexes. Cobalt(III) complexes favour a d 6 low spin
octahedral configuration and are kinetically inert. This means that the ligands are not labile
and therefore it is common to prepare the analogue Co(II) species first and convert it into the
Co(III) complex by oxidation afterwards[4]. This was done for the first part of the experiment
were first [Co(en)3]2+ was synthesized and was secondly oxidised to [Co(en)3]Cl3 by H2O2.
The three bidentate ethylenediamine ligands form three 5 membered chelate rings in the metal
complex which leads to greater stability. The tris(ethylenediamine)cobalt(III) chloride
complex has (as all octahedral metal complexes with three bidentate ligands) two enantiomers
( 'right-handed' and 'left-handed'). This enantiomers can racemate if a rearrangement over
a trigonal bipyramidal- or a square-based pyramidal intermediate takes place while one of the
bidentate ligands donor atoms is uncoordinated (cf. Fig. 1)[5].
The dinosar ligand that is produced in a
M

template synthesis in the second part of the

trigonal bipyramidal

experiment is a cryptant ligand[2]. It also

forms

three

5-membered

rings

in

[Co(dinosar)]Br3. The stability of this

M
left-handed

right-handed

complex is even greater than the stability

of [Co(en3)][Cl]3 since all donor atoms sit

in one molecule. This cage-like cryptand

square-based pyramidal
Fig. 1: Enantiomers and possibility of

ligands like dinosar can be used to formrearrangement in an octahedral metal complex

complexes with unstable metal centres[6].

with three bidentate ligands

Patrick Zwick

Exp 5

3 Experimental part
3.1 Synthesis of tris(ethylenediamine)cobalt(III) chloride

CoCl2*6H2 O

H2O2

H2 N

NH2

HCl

EtOH, H2O, 0 C, 1h

H2
H2
N H2 N
N
Cl3

Co
N N
H2 H2

N
H2

CoCl26H2O

C2H8N2

HCl

[Co(en)3]Cl3

6.00 g

4.51 mL

4.25 mL, 6M

2.09 g

25.0 mmol

67.5 mmol

25.5 mmol

7.61 mmol

1.0 eq.

2.7 eq.

1.0 eq.

30,44%

CoCl26H2O (1, 6.00 g, 25.0 mmol, 1.0 eq.) was dissolved in H2O (17.5 mL).
Ethylenediamine (2, 4.51 mL, 67.5 mmol, 2.7 eq.) and aqueous HCl (3, 6M, 4.35 mL, 25.5
mmol, 1.0 eq.) were added to H2O (12.5 mL) and cooled on ice. The aqueous CoCl2 solution
was added to the diethylenamin solution and H2O2 (5 mL, 30%) was added to this mixture
while it was constantly stirred. The mixture was placed on a heat plate and boiled gently until
there was only 30 mL left. Concentrated HCl (30 mL) and ethanol (60 mL) were added to the
mixture. The mixture was allowed to cool down to RT over 30 min. After the mixture was
cooled on ice, the precipitate was collected by filtration. The solid was washed with ethanol (2
x 10 mL) and diethyl ether (2 x 10 mL). The solid was air dried to obtain the product (4, 2.09
g, 7.61 mmol, 30%, Lit[3]: 65 %) as yellow crystals.
H-NMR (250 MHz, 298 K, DMSO-d6, /ppm): 5.90 5.59 (m, 6 H, 2), 5.48 5.17 (m, 6 H,

2), 2.82 2.55 (m, 6 H, 1), 2.54 2.44 (m, 6 H, 1).

1

H-NMR (250 MHz, 298 K, D2O, /ppm): 5.20 4.96 (m, 6 H, 2), 4.88 4.61 (m, 6 H, 2),

3.00 2.64 (m, 12 H, 1).

1a 1b
H2
2a H H
H N H2 N
N
H
2b
Co

Cl3

N N
N
H2 H2 H2

Patrick Zwick

Exp 5

3.2 Synthesis of [Co(dinosar)]Br3

NO2
H2
H2
N H2 N
N
Co

HN
1) H 2O, 40 C, 1.5h

O
Cl3

CH 3NO2

Na 2CO3 *10H 2 O

N N
N
H 2 H 2 H2

HN

NH
Br 3

Co

H 2) Acetic acid, HBr

HN

NH

NH

NO2

[Co(en)3]Cl3

Na2CO310H2O

CH3NO2

CH2O

[Co(dinosar)]Br3

1.81 g

4.05 g

5 mL

40 mL, 37 %

0.56 g

5.22 mmol

14.2 mmol

92.3 mmol

537 mmol

1.10 mmol

1.0 eq.

2.7 eq.

18 eq.

103 eq.

21,07%

[Co(en)3]Cl3 (5, 1.81 g, 5.22 mmol, 1.0 eq.) and Na2CO310H2O (6, 4.05 g, 14.2 mmol, 2.7
eq.) were dissolved in water (90 mL). Acetonitrile (7, 5 mL, 92.3 mmol, 18 eq.) and
formaldehyde (8, 47 %, 40 mL, 537 mmol, 103 eq.) were added and the mixture was briefly
stirred. The mixture was heated to 40 C for 1.5 h without stirring. The solution was stirred
with a glass rod to induce crystalisation. The solution was cooled on ice and the precipitate
was collected by filtration. The solid was dissolved with hot acetic acid (1M, 30 mL) and
concentrated HBr (15 mL) was added immediately to the yellow solution. The solution was
allowed to cool down to RT. The precipitate was collected by filtration, washed with MeOH /
H2O (1:1, 1 x 15 mL), MeOH (1 x 15 mL), diethyl ether (1 x 15 mL) and was air dried to
obtain the product (9, 0.56 g, 1.10 mmol, 21 %, Lit:[1]: 55 % ) as orange solid.
H-NMR (250 MHz, 298 K, D2O, /ppm): 3.88 (dd, 2JHH = 13.7, 1.7 Hz 6 H, 1), 3.57 (dd,

1
2

JBH = 11.7, 9.1 Hz, 6 H, 2), 3.36 (dd, 2JHH = 13.9, 2.0 Hz, 6 H, 1), 2.94 (dd, 2JBH = 11.7,

9.2 Hz, 6 H, 2).

1b

1a NO2
H
H

2a
H HN
NH
HN
H
2b
Co
HN

NH

Br3

NH

NO2

Patrick Zwick

Exp 5

4 Discussion

CoCl2*6H2 O

H2O2

H2 N

NH2

HCl

EtOH, H2O, 0 C, 1h

H2
H2
N H2 N
N
Cl3

Co
N N
H2 H2

N
H2

4
NO2
H2
H2
N H2 N
N

Co

HN
O
Cl3

Na2CO3 *10H2 O

CH3NO2

N N
N
H2 H2 H2

1) H2O, 40 C, 1.5h

NH
Br 3

Co

H 2) Acetic acid, HBr

HN

HN

NH

NH

NO2

The synthesis (A) of tris(ethylenediamine)cobalt(III) chloride (4) was done as described in the
reference[3]. Three ethylenediamine ligands were coordinated to a cobalt atom to form
[Co(en)3]Cl2 which was then oxidised by H2O2 to form the product [Co(en)3]Cl3 (4). For the
interpretation of the 1H-NMR spectra the protons had to be separated in two groups:
homotope and diastereotope. It was shown that the protons bonded to the nitrogen atoms (1)
and the protons bonded to cabon atoms (2) are diastereotope. So all protons are diastereotope.
This comes by the chirality since the ethylendiamine ligands can coordinate to the metal
centre forming or isomers. The DMSO-d6 spectrum shows four multiplets with integrals
of each 6 protons due to the diastereotope protons. The D2O shows only three multiplets
because the signals of 1a and 1b comes out as one signal with an integral of 12 protons. The
integrals of the reference peak overlapped signals could be worked out by a comparison of the
two spectra which actually was the reason for measuring the product in two solvents. The
multiplets at 2.82 2.55 ppm and 2.54 2.44 ppm in The DMSO-d6 spectrum respectively
3.00 2.64 ppm in the D2O spectrum belongs to the diastereotope protons bonded to the
nitrogen atoms (1a + 1b). The other two multiplets belong to the diastereotope protons (2a +
2b). The signals could not been differentiated to the protons (2a) and (2b) respectively (1a)
and (1b) because there is to less information with only these 1H-NMR spectra. The non
binomial triplet at 7.23 ppm belongs to some free protonated ethylenediamines which are not
coordinated to the metal.
The synthesis (B) of [Co(dinosar)]Br3 (9) also went well. This experimental part (B) was done
as described in the reference[1]. For the interpreatation of the 1H-NMR spectrum, the protons
5

Patrick Zwick

Exp 5

had to be separated in diastereotope an homotope again. It was shown that all protons bonded
to a carbon atom (1a, 1b, 2a, 2b) are diastereotope and the protons bonded to a nitrogen atom
do not even give a signal since they are exchanged by deuterium quickly. The 1H-NMR
spectrum shows four doublets of doublets. The literature[1,2] showed that the peak at -11 ppm
belongs to the former carbon atoms of ethylenedyamine and the peak at -15 ppm belongs to
the bridging carbon atoms. The peak at 22 ppm in the HMQC spectrum belongs to the carbon
carrying the nitro groups since it does not show any proton correlation. The proton signals at
3.88 ppm and 3.36 ppm (1a and 1b) correlate with the carbon signal at -11 ppm in the HMQC
spectrum. This correlation shows that this protons sit at the bridging carbon atoms. The proton
signals at 3.57 ppm and 2.94 ppm (2a and 2b) correlate with the carbon peak at -15 ppm in the
HMQC spectrum. Therefore this protons sit at the former carbon atoms of ethylendiamine.
The COSY spectrum shows that the proton signals at 3.88 ppm and 3.36 ppm (1a and 1b) are
correlating and that the proton signals at 3.57 ppm and 2.94 ppm (2a and 2b) are correlating.
This information shows that the diastereotope protons that sit on the same carbon atom are
coupling to each other. The measured coupling constants confirm that theory since the
coupling constants of the signals at 3.88 ppm and 3.36 ppm (1a and 1b) are the same and the
coupling constants of the signals at 3.57 ppm and 2.94 ppm (2a and 2b) are the same, too. The
signals of the diastereotope protons (1a, 1b and 2a, 2b) could not be differentiated with this
spectrum.
5 Conclusion
The aim of the experiment was reached. The synthesis of tris(ethylendiamine)cobalt(III)
chloride and the conversion of the ligand to dinosar to build the final product [Co(dinosar)]Br3
went well. The purity of the products were proved by 1H-NMR spectroscopy and the data was
discussed. All questions were answered and attached.

6 References
[1]

Harrowfield et al., J. Chem. Educ., 1985, 62, 804.

[2]

C. E. Housecroft, Task Sheet Experiment 5, 2014, 2 3.

[3]

Krause et al., J. Chem. Educ., 1976, 53, 667.

[4]

C. E. Housecroft, A. G. Sharpe, Inorganic Chemistry, Pearson, Harlow, 2012, 744

756.

Patrick Zwick

Exp 5

[5]

C. E. Housecroft, A. G. Sharpe, Inorganic Chemistry, Pearson, Harlow, 2012, 991

[6]

Geue et al., J. Am. Chem. Soc., 1984, 106, 5478.

7 Answers to the questions

7.1 The reaction to make [Co(dinosar)]3+ is an example of a template synhtesis. Explain
what this means.
When the reactants are hold together in a template, so that a combination of them is allowed
without many side reactions, it is called a template synthesis. In the specific case of this
synthesis it was the NH2 groups of ethylenediamine that are coordinated by the cobalt centre
close to each other in the tris(ethylenediamnie)cobalt(III) chloride template that react with
nitromethane and formaldehyde to give the dinosar ligand in the final product.
7.2 Explain why the stability of the following complexes decrease in the order:
[Co(dinosar)]3+ > [Co(en)3]3+ > [Co(NH3)6]3+
The dinosar and the ethylenediamine ligands form chelating rings in the metal complex.
Therefore this complexes are more stable than the ammonio complex since this ligand does
not chelate at all. The complex with the dinosar ligand is more stable than the
tris(ethylendiamine)cobalt complex because all six coordinated groups sit in the same
molecule instead of three molecules as in [Co(en)3]3+. The dinosar ligand is quite inflexible
and therefore more immutable in contrast to ethylenediamine. This effect also decreases from
[Co(en)3]3+ to [Co(NH3)]3+. This is an entropie effect since e.g. six molecules get free but only
three molecules get bonded to the complex in the ligand exchange from [Co(NH 3)]3+ to
[Co(en)3]3+.
7.3 What types of isomers could the following compounds show? Not all complexes
possess isomers. Draw the structures of all isomers and give names that tell the isomers
apart (e.g. cis and trans).
- octahedral [Rh(ox)3]3-

- square planar [PtBr2(NMe3)2]

- octahedral [TiCl3(THF)3]

- octahedral [Ir(acac)3]

- square planar [Rh(CO)(PPh3)2Cl]

- octahedral [Ru(bpy)3]2+

- octahedral [Ru(phen)2Cl2]

- tetrahedral [CoCl2Br2]27

Patrick Zwick

Exp 5

O
O

O
O

O
O

Rh

Rh

O
O

Br

Br

Cl
Cl

Ti

Ti

Me3 N

NMe3

Br

Cl

Cl

Pt

Br
NMe3

trans
O

O
Ir

NMe3

cis

O
Cl

Pt

Ir

O
O

Cl

fac

mer

2
N

N
N

OC

Cl

Rh

Ph3P

OC

PPh3

Ph3 P

cis

Ru
N

PPh 3

N
N

Cl

Cl

Cl

Ru

N
N
N

N
N

Ru

Cl

cis +

cis +

Cl

Cl

Co
Cl

trans

Cl

trans

N
Cl

Rh

N
Ru

Ru

Br
Br

no isomers

8. Spectra
The experimental spectra are attached to this protocol as followed:
8.1 250 MHz 1H-NMR spectrum of [Co(en)3]Cl3 in DMSO-d6 (p. 9).
8.2 250 MHz 1H-NMR spectrum of [Co(en)3]Cl3 in D2O (p. 10).
8.3 250 MHz 1H-NMR spectrum of [Co(dinosar)]Br3 in D2O (p. 11).

5500

5.32

5.74

6000

2.82
2.69
2.54
2.50
2.44

5.90
5.74
5.59
5.48
5.32
5.17

ac_praktI_.2900.1.fid
PZ Exp5 [Co(en)2][(Cl)]3 in dmso-d6

400
5000

5.4

6.00

5.6
5.5
f1 (ppm)

5.3

200

4500

100

4000

3500

5.2

2.50

5.7

2.54

5.8

2.69

5.9

6.00

300

3000
1000

2500

800

2000

600
400

1500

200

2.75

2.70

16.13

2.80

1000

2.65 2.60
f1 (ppm)

2.55

2.50

500

2.45

11.5 11.0 10.5 10.0

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

16.13

6.00

6.00

5.5 5.0
f1 (ppm)

4.5

4.0

3.5

3.0

2.5

-500
2.0

1.5

1.0

0.5

0.0

-0.5

2.64

3.00

5.20
5.08
4.96
4.88
4.61

3000
2800

4.61

4.88

4.96

5.08

5.20

ac_praktI_.2892.1.fid

300

2600
2400

200

2200

100

4.9 4.8
f1 (ppm)

4.7

1800

4.6
2.64

5.0

15.22

5.1

3.00

5.2

6.00

2000

1600

400

1400

300

1200

200

1000

100

800

12.02

600

3.00 2.95 2.90 2.85 2.80 2.75 2.70 2.65

f1 (ppm)

400
200

11.5 11.0 10.5 10.0

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5 5.0
f1 (ppm)

-200

12.02

15.22

6.00

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

-0.5

-1.0

2.99
2.95
2.92
2.88

3.39
3.38
3.34
3.33

3.63
3.59
3.56
3.52

3.92
3.92
3.87
3.86

3.92
3.92
3.87
3.86
3.63
3.59
3.56
3.52
3.39
3.38
3.34
3.33
2.99
2.95
2.92
2.88

ac_praktI_.2916.1.fid
PZ exp5 [Co(dinosar)][Br]3 in D2O
1H NMR (250 MHz, Deuterium Oxide) 3.88 (dd, J = 13.7, 1.7 Hz, 7H), 3.57 (dd, J = 11.7, 9.1 Hz,
6H), 3.36 (dd, J = 13.9, 2.0 Hz, 6H), 2.94 (dd, J = 11.7, 9.2 Hz, 6H).

3600
3400
3200

1400

3000

1200

2800
2600

1000

2400

800

2200

600

2000

B (dd)
3.57
A (dd)
3.88

400

1800

D (dd)
2.94

1600

C (dd)
3.36

200

1400
1200

3.9

3.8

3.7

3.6

3.5

1000

6.00

6.03

6.01

6.00

0
3.4 3.3
f1 (ppm)

3.2

3.1

3.0

800

2.9

600
400

12.0 11.5 11.0 10.5 10.0

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5 5.0
f1 (ppm)

4.5

4.0

3.5

6.00 6.00

6.00 6.99
6.01 5.83
6.03 6.41

200

3.0

-200
2.5

2.0

1.5

1.0

0.5

0.0

-0.5

-1.0