The Synthetic of Cis and Trans Pottasium Dioxalatodiaquochromate (III)

Mutia Salsabila Syaifuddin

1813442011
ICP of Chemistry Education / IV
St. Aminah Y
Suriati Eka Putri, S.Si., M.Si
 APPROVAL SHEET

Complete report of Inorganic Chemistry I Experiment, which entitle “The

Synthetic of Cis and Trans Pottasium Dioxalatodiaquochromate (III)” arranged
by:
name : Mutia Salsabila Syaifuddin
ID : 1813442011
class/group : ICP of Chemistry Education / IV (Four)
it has been checked well by Assistant and Assistant Coordinator and acceptable.

Makassar, April 2020

Assistant Coordinator Assistant

A. Cici Kurnia Abidin, S. Si St. Aminah Y

ID. 1513440008

Known by
Responsibility Lecture

Suriati Eka Putri, S.Si., M.Si

ID. 1988030520122002
A. TITLE OF EXPERIMENT
The Synthetic of Cis and Trans Pottasium Dioxalatodiaquochromate (III)

B. OBJECTIVE OF EXPERIMENT
To learn about the synthetic and the properties of isomerism cis and trans
from potassium dioxalatodiaquochromate (III) complex salt.

C. LITERATURE REVIEW
1. General Background
The transition metals have always held a special interest for inorganic
chemists. Whereas the compounds of the main group metals are almost always
white, the transition metal compounds come in every color of the rainbow.
Chemists were fascinated by the fact that it was sometimes possible to make
compounds of the same formula but in different colors. Inorganic chemists
generally restrict the term transition metal to an element that has at least one
simple ion with an incomplete outer set of d electrons. For example, chromium
has two common oxidation states (plus several other less common ones). The +3
oxidation state has a partially filled d set even though the +6 state has an empty d
set (Canham. 2010).
An important point that must not be forgotten is that d-block metal atoms
are, of course, many-electron species, and when we discuss, for example, radial
distribution functions of the n-d atomic orbitals, we refer to hydrogen like atoms
and, therefore, the discussion is extremely approximate. Nearly all the d-block
metals are hard, ductile and malleable, with high electrical and thermal
conductivities. With the exceptions of Mn, Zn, Cd and Hg, at room temperature,
the metals possess one of the typical metal structures. Metals of the d-block are
(with the exception of the group 12 metals) much harder and less volatile than
those of the s-block (Housecroft. 2005).
Transition metal complexes have a wide range of shapes. With four
ligands, there are two alternatives: tetrahedral and square planar. Tetrahedral are
more common in Period 4 transition metals, and square planar complexes are
more prevalent among Periods 5 and 6. The tetrahedral geometry of the
tetrachlorocobaltate(II) ion, (Canham. 2010)
The number of ligands in a complex depends on the size of the metal
atom, the identity of the ligands, and the electronic interactions. The coordination
number of a metal atom or ion is not always evident from the composition of the
solid, as solvent molecules and species that are potentially ligands may simply fill
spaces within the structure and not have any direct bonds to the metal ion. For
example, X-ray diffraction shows that CoCl2.6H2O contains the neutral complex
[CoCl2(OH2)4] and two uncoordinated (outer-sphere) H2O molecules occupying
well-defined positions in the crystal. Such additional solvent molecules are called
solvent of crystallization (Shriver, et al. 2014).
The metal–ligand bonding in complexes can generally be considered in
terms of σ-donor ligands interacting with a metal centre which acts as a σ-
acceptor. This may, in some complexes, be augmented with interactions involving
п-donor ligands or -acceptor ligands. Examples of coordination number 2 are
uncommon, being generally restricted to Cu(I), Ag(I), Au(I) and Hg(II), all d10
ions. Examples include [CuCl2]-. the sterically demanding amido groups force a 2-
coordinate environment on a metal centre that usually prefers to be surrounded by
a greater number of ligands (Housecroft. 2005).
We rarely encounter a “naked” transition metal ion, because the ion is
usually covalently bonded to other ions or molecules. These groupings are called
metal complexes, and it is the number and diversity of the metal complexes that
provide the wealth of transition metal chemistry. We now refer to this number (or
numbers) as the coordination number(s) of the metal ion, and it is usually 4 or 6.
The molecules or ions that are covalently bonded to the central metal ion are
called ligands. There are few simple complexes with five ligands, but it is
interesting to find that, like the four-ligand situation, these complexes have two
stereochemistries: trigonal bipyramidal, like the main group compounds, and
square-based pyramidal (Canham. 2010).
Ionization isomers result from the interchange of an anionic ligand within
the first coordination sphere with an anion outside the coordination sphere.
Hydration isomers result from the interchange of H2O and another ligand between
the first coordination sphere and the ligands outside it. Coordination isomers are
possible only for salts in which both cation and anion are complex ions; the
isomers arise from interchange of ligands between the two metal centres. Linkage
isomers may arise when one or more of the ligands can coordinate to the metal ion
in more than one wa. Polymerization’ isomerism is a rather unfortunate term since
we are actually not dealing with polymeric structures. Polymerization isomers
denote complexes which have the same empirical formulae but different
molecular masses (Housecroft. 2005).
Isomers can be categorized as structural isomers and stereoisomers. For
stereoisomers, the bonds to the metal ion are identical, whereas the bonds of
structural isomers are different. Structural isomerism has four common types:
linkage isomerism, ionization isomerism, hydration isomerism, and coordination
isomerism. Ionization and hydration isomerism are sometimes categorized
together as coordination-sphere isomerism because in both cases it is the identity
of the ligands that differs (Canham. 2010).
Optical isomerism is concerned with chirality, and some important terms
relating to chiral complexes. Enantiomers are a pair of stereoisomers that are
nonsuperposable mirror images. d and l prefixes: sometimes (+) and (-) are
denoted by dextro- and laevo- (derived from the Latin for right and left) and these
refer to right- and left-handed rotation of the plane of polarized light respectively;
dextro and laevo are generally abbreviated to d and l. The +/- or d/l notation is not
a direct descriptor of the absolute configuration of an enantiomer (the arrangement
of the substituents or ligands) for which the following prefixes are used. R and S
prefixes: the convention for labelling chiral carbon atoms (tetrahedral with four
different groups attached) uses the Cahn–Ingold–Prelog notation. The four groups
attached to the chiral carbon atom are prioritized according to the atomic number
of the attached atoms, highest priority being assigned to highest atomic number,
and the molecule then viewed down the C_X vector, where X has the lowest
priority. The R- and S-labels for the enantiomers refer to a clockwise (rectus) and
anticlockwise (sinister) sequence of the prioritized atoms, working from high to
low (Housecroft. 2005). low (Housecroft. 2005). low (Housecroft. 2005).
2. Result of Review
Distinguishing between cis- and trans-isomers of a square planar complex
or between mer- and fac-isomers of an octahedral complex is most
unambiguously confirmed by structural determinations using single-crystal X-ray
diffraction (Housecroft. 2005).
Synthesis of K[Cr(C2O4)2(H2O)2].2H2O was carried out through two
different synthesis techniques turned out to produce two solids of complex
compounds different. In the first method, red-purple solids are produced, whereas
the second method produces solids purple. Characteristics of the presence of deep
oxalate ions complex compounds can be observed from the spectrum
infrared. (Kurnia,et al. 2006).
The cis -K[Cr(C2O4)2(OH2)2] and trans -K[Cr(C2O4)2(OH2)2]·3H2O
complexes were synthesized according to the method of Werner and his
coworkers. The TG–MS analysis confirmed the thermodynamic stability of the
synthesized isomers and it shows that the trans-K[Cr(C2O4)2(OH2)2]·3H2O is
more stable in the solid state than cis-K[Cr(C2O4)2(OH2)2].Moreover, both
isomers undergo dehydration and decarboxylation (Drezezdron. 2018).
However, both the isomers exist as an equilibrium mixture. But in an
ethanolic solution at around 70oC, the cis isomer precipitates much quicker
compared to the trans isomer, and hence leading to a shift in equilibrium away
from trans, with producing only cis isomer. Cis isomer is the kinetically favored
product whereas trans isomer is thermodynamically more stable. The trans isomer
can be produced by converting the cis isomer by supplying heat energy at 180°C
for time of 15 minutes. Solid phase synthesis of the trans isomer was also
reported (Biswas. 2017).
Instability of complex compounds K[Cr(C2O4)2(H2O)2].2H2O can not only
be observed in aqueous solution, but can also observed using time parameters. At
the beginning of synthesis, red and purple solids are produced shiny, which is
already known is complex compound trans-K[Cr(C2O4)2(H2O)2].2H2O. Five
months later, the solid color is red shiny purple has changed its color to purple.
This shows that the compound complex trans-K[Cr(C2O4)2(H2O)2].2H2O is
relative unstable compared to its isomer, cis- K[Cr(C2O4)2(H2O)2].2H2O. Like any
compound unstable mononuclear oxalate complex (Kurnia,et al. 2006).

D. APPARATUS AND CHEMICAL

1. Apparatus
a. Beaker glass 100 mL 1 piece
b. Beaker glass 250 mL 1 piece
c. Funnel 1 piece
d. Vaporizer cup 1 piece
e. Vacum pump 1 piece
f. Buchner funnel 1 piece
g. Maesuring flask 50 mL 1 piece
h. Erlenmeyer 100 mL 1 piece
i. Erlenmeyer 250 mL 1 piece
j. Spray Bottle 1 piece
k. Analytical balence 1 piece
l. Drop pipette 1 piece
m. Spatula 2 piece
n. Watch glass 2 piece
o. Stir bar 2 piece
p. Spoon 1piece
q. Gauze and Tripod 1 Set
r. Rough cloth 1 piece
s. Smooth cloth 1 piece
2. Chemicals
a. Oxalic acid dyhidrat (H2C2O4.2H2O)
b. Potassium dichromate (K2Cr2O7)
c. Etanol (C2H5OH)
d. Aquades (H2O)
e. Filter paper
 f. Whatman filter paper
g. Match
h. Tissue

E. WORK PROCEDURES
1. Preparation of isomer trans-potassium dioxalatodiakuocromate
2. Preparation isomer of cis-potassium dioxalatodiakuocromate

3. Testing of isomer purity

Trans crystal Little of

Isomer of trans
ammonia

F. OBSERVATION RESULTS
1. Preparation of Trans Isomer Potassium Dioxalatodiaquochromate(III)
No. Activities Results
1. Weighed K2Cr2O7 4, 0017 gram
2. Weighed H2C2O4 12, 0018 gram
3. Solveded K2Cr2O7 Solution color orange
4. solveded H2C2O4 Solution become cololess
 Mix K2Cr2O7 (orange) and
5. Solution become black
H2C2O4 (colorless) solution
solution evavoration till ½
6. 35 mL
(half)
7. solution evavoration till 1/3 11, 67 mL
8. Filter solution Not crystal formed
Wash crystal with H2O and
9. -
C2H5OH
10. Dry Crystal -
10. Weight crystal -
2. Preparation of Cis Isomer Potassium Dioxalatodiaquochromate(III)
No. Activities Results
1. Weighed K2Cr2O7 4, 002 gram
2. Weighed H2C2O4 12, 001 gram
Mix K2Cr2O7 and H2C2O4 with 3
3. Solution black with buble
drop H2O
black Solution added C2H5OH
4. Three are precipation black
20 Ml
Solution dekantir and filter
5. Black precipitation
with vacum pump
6. Weighed crystal 2,005 gram
3. Purity of Isomer Test
No. Activities Results
Crystalstrans potassium
1. dioklasalatodiakuocromat (III) -
reaction wirh 3 drops NH3
Crystalstrans potassium
2. dioklasalatodiakuocromat (III) Green
reaction wirh 3 drops NH3

G. DATA ANALYSIS
Known : m H2C2O4.2H2O cis = 12,001 gram
m H2C2O4.2H2O trans = 12, 0018 gram
m K2Cr2O7 cis = 4,002 gram
m K2Cr2O7 trans = 4,0017 gram
Mr H2C2O4.2H2O = 126 gr/mole
Mr K2Cr2O7 = 294 gr/mole
m practice of trans- = 0 grams
m practice of cis- = 2, 005 grams
Ask : %rendement = ?
Answer :
1. Rendement of trans
mass
n H2 C2 O4 . 2H2 O =
Mr
12, 0018 gram
= gram
126
mole
= 0.0952 mole
mass
n K 2 Cr2 O7 =
Mr
4, 0017 gram
= gr
294
mole
= 0.0136 mole
K2Cr2O7 (aq) + 7H2C2O4.2H2O (aq) → 2K [Cr(H2O)2(C2O4)2] (g) + 6CO2 +
17H2O (g)
0.0136 mole 0.0952 mole - - -
0.0136 mole 0.0952 mole 0.0272 mole 0.0816 mole 0.2312mole
- - 0.0272 mole 0.0816 mole 0.2312mole

Mass K [Cr(H2O)2(C2O4)2] theory = mole × Mr

= 0.0272 mole × 303 gr/mole
= 8.2416 gram
Rendemen Trans:
 mass practice
% trans K [Cr(H2O)2(C2O4)2] = × 100%
mass theory
0
= 8.2416 gram × 100%

=0%

2. Rendement of Cis
mass
n H2 C2 O4 . 2H2 O =
Mr
12, 001 gram
= gram
126
mole
= 0.0952 mole
mass
n K 2 Cr2 O7 =
Mr
4, 002 gram
= gr
294
mole
= 0.0136 mole
K2Cr2O7 (aq) + 7H2C2O4.2H2O (aq) → 2K [Cr(H2O)2(C2O4)2] (g) + 6CO2 +
17H2O (g)
0.0136 mole 0.0952 mole - - -
0.0136 mole 0.0952 mole 0.0272 mole 0.0816 mole 0.2312mole
- - 0.0272 mole 0.0816 mole 0.2312mole

Mass K [Cr(H2O)2(C2O4)2] theory = mole × Mr

= 0.0272 mole × 303 gr/mole
= 8.2416 gram
mass practice
% cis K [Cr(H2O)2(C2O4)2] = × 100%
mass theory
2,005 gram
= 8.2416 gram × 100%

= 24,32 %

H. DISCUSSION
Salah satu aspek menarik dari senyawa kimia koordinasi adalah kemungkinan
keberadaan isomer. Isomer suatu senyawa mengandung jumlah dan jenis atom
yang sama, tetapi mereka memiliki struktur yang berbeda. Beberapa jenis
isomerisme telah ditunjukkan, tetapi hanya beberapa jenis yang paling penting
yang akan dijelaskan di sini. Jenis isomer geometri yang paling umum melibatkan
isomer cis dan trans dalam bidang kuadrat dan oktahedral. Jika kompleks MX2Y2
adalah tetrahedral, hanya ada satu isomer karena semua posisi dalam tetrahedral
adalah setara. Jika MX2Y2 kompleks adalah kuadrat persegi, isomer cis dan trans
dimungkinkan (House. 2008).
1. Pembuatan isomer trans-kalium dioksalatodiakuokromat (III)
Percobaan ini bertujuan untuk pembuatan suatu isomer yaitu isomer trans-
kalium dioksalatodiakuokromat (III). Adapun bahan dasar yang digunakan dalam
percobaan ini adalah Kristal asam oksalat dan Kristal kalium dikromat. Mula-
mula Kristal asam oksalat yang berwarna putih dilarutkan dalam sedikit mungkin
aquadest panas sehingga menghasilkan. begitu juga dengan Kristal kalium
dikromat yang berwarna orange dilarutkan dalam sedikit mungkin aquadest panas.
Penambahan akuades ini bertujuan untuk mempercepat terjadinya reaksi antara
reaktan karena K[Cr(H2O)2(C2O4)2] memiliki tingkat kelarutan yang tinggi
sehingga untuk membuatnya, reaktan terlebih dahulu dilarutkan sehingga
kesetimbangan bergeser ke arah trans.
K2Cr2O7 + 2H2O 2K+ + Cr2O7 2-

H2C2O4.2H2O + 2H2O 2H+ + C2O4 2- + 2H2O

Larutan dari kedua Kristal ini kemudian dicampurkan dalam suatu gelas
kimia dan ditutup dengan kaca arloji sehingga menghasilkan perubahan warna
dari asam oksalat berwarna putih ditambah kalium dikromat berwarna orang
menghasilka larutam berwarna hitam. proses terjadinya perubahan warna dari
orange dan putih menjadi coklat ini karena terbentuknya senyawa kompleks
kalium dioksalatodiakuokromat, dimana dalam senyawa kompleks tersebut dua
macam ligan dan satu atom pusat dari logam transisi. Sedangkan tujuan gelas
kimia ditutup untuk mencegah agar CO2 dan H2O tidak menguap, karena apabila
CO2 dan H2O menguap maka yang terbentuk adalah cis bukan trans. Jenis reaksi
yang terjadi yaitu reaksi redoks. Adapun reaksi yang terjadi yaitu:
 2-
Cr2O7 + 2H+ + 6e Cr3+ + 7H2O x1
C2O4 2- 2CO2 + 2 e x2
2-
Cr2O7 + C2O4 2- + 14H+ 2 Cr3+ + 6CO2 + 7H2O
Reaksi lengkap yaitu:
K2Cr2O7(aq) + 7 H2C2O4. 2 H2O(aq) 2 K[Cr(H2O)2(C2O4)2](s) + 6 CO2(g)↑+
17 H2O(l)
Larutan kemudian diuapkan hingga volume setengahnya dan kemudian
diuapkan lagi pada suhu kamar hingga volumenya tinggal sepertiga dari volume
awal dan melanjutkan penguapan pada suhu kamar. Tujuannya adalah agar H2O
atau air yang tidak diperlukan atau tidak diinginkan bisa habis dan tidak
mempengaruhi pembentukan senyawa kompleks kalium dioksalatodiakuokromat,
karena senyawa kompleks tersebut hanya mengandung 2 molekul H2O dan 2
molekul C2O42- sebagai ligan dan kalau dalam larutan tersebut masih banyak
mengandung H2O atau air kemungkinan ligan H2O bertambah jumlahnya yaitu
lebih dari yang dinginkan sehingga untuk menghindari itu diperlukan penguapan.
Setelah diuapkan, larutan kemudian disaring. Namun terjadi kesalahan dalam
praktikum sehingga tidak terbentuk kristal karena disebabkan pada pelarutan
K2Cr2O7 dan H2C2O4.2H2O seharusnya menggunakan pelarut aquades yang hanya
sedikit serta dilakukan pendinginan dengan air es sebelum melakukan
penyaringan. Hibridisasi K[Cr(C2O4)2(H2O)2] adalah :
24Cr = [Ar] 4s1 3d5
3+
24Cr = [Ar] 4s0 3d3
Keadaan dasar:

3d3 4s0

Cr dalam K[Cr(H2O4)2(H2O)2]:

3d 4s 4p

2H2O (ligan) 2C2O4 (ligan)

Hibridisasi =d2sp3
Adapun geometri K[Cr(C2O4)2(H2O)2] adalah berdasarkan teori (ramlawati,2015)
bahwa semua senyawa kompleks yang memiliki bilangan koordinasi 6 dengan
jenis hibridisasi d2sp3memiliki bentuk oktahedral.
O
C OH
O O
C

O OH2
HO
K Cr OH
H2O O

C
O
O
C
HO
O

Trans-kalium dioksalatodiakuokromat (III)

2. Pembuatan isomer cis-kalium dioksalatodiakuokromat (III)

Pada percobaan ini mengunakan bahan dasar yang sama dengan bahan
dasar dari pembuatan isomer trans yaitu kalium dikromat dan asam oksalat. Mula-
mula, kedua dari Kristal ini dicampurkan hingga homogen. Pencampuran ini
dilakukan tanpa pelarutan dengan air terlebih dahulu. Pada saat pencampuran ini,
terjadi kontak dengan udara yang mengandung uap air sehingga campuran dari
Kristal kalium dikromat dan Kristal asam oksalat yang awalnya berwarna orange,
lama kelamaan, ditambahkan setetes air sehingga menghasilkan warna hitam.
Penambahan satu tetes H2O berguna untuk menggeser kesetimbangan cis ↔ trans
ke arah cis karena cis - K[Cr(H2O)2(C2O4)2] memiliki kelarutan yang
rendah sehingga kristalnya dapat diperoleh………………………………………..
Setelah itu Kristal ditambahkan dengan etanol dengan tujuan agar air
yang terbentuk sebagai produk samping yang belum menguap dapat terikat
dengan etanol sehingga air tesebut menguap bersama etanol. Setelah terbentuk
endapan Kristal yang padat, Kristal kemudian disaring dengan menggunakan
pompa vakum denga tujuan untuk menyempurnakan penyerapan air. Pada proses
penyaringan, Kristal dicuci dengan etanol dengan tujuan untuk memurnikan
kristal. Kristal yang diperoleh berarna hitam kemudian dikeringkan dan ditimbang
sehingga diperoleh berat Kristal sebesar 2,005 gram. Reaksi yang terjadi yaitu:
 2-
Cr2O7 + 2H+ + 6e Cr3+ + 7H2O x1
C2O4 2- 2CO2 + 2 e x2
2-
Cr2O7 + C2O4 2- + 14H+ 2 Cr3+ + 6CO2 + 7H2O
Reaksi lengkap yaitu:
K2Cr2O7(aq) + 7 H2C2O4. 2 H2O(aq) 2 K[Cr(H2O)2(C2O4)2](s) + 6 CO2(g)↑+
17 H2O(l)
hibridisasi yang menjelaskan tentang 2 K[Cr(C2O4)2(H2O)2] adalah:
24Cr = [Ar] 4s1 3d5
3+
24Cr = [Ar] 4s0 3d3
Keadaan dasar:

3d3 4s0

Cr dalam K[Cr(H2O4)2(H2O)2]:

3d 4s 4p

2H2O (ligan) 2C2O4 (ligan)

Hibridisasi =d2sp3
Struktur geometri dari K[Cr(H2O4)2(H2O)2] yang memiliki 6 bilangan koordinasi
dan hibridisasi d2sp3 adalah oktahedral:
O
HO C
O O
C

H2O O
K Cr
OH

H2O O OH
C O
O
HO C
O

Cis-kalium dioksalatodiakuokromat (III)

3. Uji kemurnian isomer

Uji ini bertujuan untuk membedakan yang mana isomer cis kalium
dioksalatodiakuokromat dan isomer transnya. Uji kemurnian terhadap isomer
dilakukan dengan penambahan ammonia encer pada Kristal yang diperoleh.
Namun, pada percobaan pembuatan isomer trans tidak terbentuk kristal.
Berdasarkan pengamatan yang telah dilakukan diperoleh Kristal cis larut dalam
amonia dan menyebar serta berwarna hijau. Sehingga dalam percobaan ini
diperoleh Kristal yang diinginkan karena menurut teori apabila Kristal cis melarut
dan menyebar serta warnanya hijau setah ditambahkan amonia.

I. CONCLUSIONS AND SUGGESTIONS

1. Conclusions
Synthesis cis isomer and trans-potassium dioxalatodiakuochromat (III) can
be done by reacting K2Cr2O7 and H2C2O4. 2H2O. Trans isomers can not react with
NH4OH because it has a steric (stable) effect. Trans isomers will form light brown
solids that remain insoluble. While cis isomer can react with NH4OH because it
does not have a steric effect (unstable). The cis isomer will form a dark green
solution which quickly spreads on filter paper. The yield obtained for cis is 24,32
% with a weight of 2,005 grams, while trans is not obtained by crystals.
2. Suggestions
It is expected that the practitioner be more careful in carrying out every
step of the work so that the yield of each step of the work of the final rendement is
obtained more.
 BIBLIOGRAPHY

Atkins, Peter, Tina Overton, Jonathan Rourke, et al. 2010. Shriver and Atkins'
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Routes of Synthesis of cis and trans Isomers of Bis(glycinato)copper(II)
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Canham, Geoff Rayner and Tina Overton. 2010. Descriptive Inorganic Chemistry
Fifth Edition. New York : W. H. Freeman and Company.

Catherine E. Housecroft and Alan G. Sharpe. 2005. Inorganic Chemistry Second

Edition. England : Pearson Education Limited.

Drzezdzon , Joanna, Lech Chmurzyn´ Ski And Dagmara Jacewicz. 2018.

Geometric isomerism effect on catalytic activities of
bis(oxalato)diaquochromates(III) for 2-chloroallyl alcohol
oligomerization. J. Chem. Sci. Vol. 130. No. 116.

Kurnia, Kiki Adi, Djulia Onggo, Dave Patrick, and K. L. Stevenson. 2006.
Sintesis Senyawa Kompleks K[Cr(C2O4)2(H2O)2].2H2O dan [N(n-
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Scanned by CamScanner
Scanned by CamScanner
 DOCUMENTATION

1. Preparation of isomer trans-potassium dioxalatodiakuocromate

Dissolve with a little

12 gram of H2C2O4 aquadest

Mix of H2C2O4 and K2Cr2O7 Dissolve K2Cr2O7

Let it at room temperature

Heated until ½ volume
 Filtrated

2. Preparation isomer of cis-potassium dioxalatodiakuocromate

Mix of H2C2O4 and Add 1-2 drop Closed with wacth

K2Cr2O7 aquadest glass

Decantir Add ethanol

 Filtrate with
Add ethanol again bunchner funnel

3. Purity of Isomer Test

Cis Crystal

Little of Amonia

Isomer of Cis
Shriver & Atkins’

W. H. Freeman and Company

New York
Shriver and Atkins' Inorganic Chemistry, Fifth Edition
© 2010 P.W. Atkins, T.L. Overton, J.P. Rourke, M.T. Weller,
and F.A. Armstrong
All rights reserved.

ISBN 978–1–42–921820–7

Published in Great Britain by Oxford University Press

This edition has been authorized by Oxford University Press for sale in the
United States and Canada only and not for export therefrom.
First printing
W. H. Freeman and Company,
41 Madison Avenue, New York, NY 10010
www.whfreeman.com
 Constitution and geometry 203

μ-oxido-bis(pentamminecobalt(III)) (12). If the number of centres bridged is greater than

two, a subscript is used to indicate the number; for instance a hydride ligand bridging
three metal atoms is denoted μ3-H. Bite
angle
A note on good practice The letter  is also used to indicate the number of points of attachment: thus
a bidentate ethylenediamine ligand bound through both N atoms is indicated as 2N. The letter  (eta)
is used to indicate bonding modes of certain organometallic ligands (Section 22.4).

Square brackets are used to indicate which groups are bound to a metal atom, and should
be used whether the complex is charged or not; however, in casual usage, neutral complexes
and oxoanions are often written without brackets, as in Ni(CO)4 for tetracarbonylnickel(0)1 10
and MnO
4 for tetraoxidomanganate(VII) (‘permanganate’). The metal symbol is given first,
then the ligands in alphabetical order (the earlier rule that anionic ligands precede neutral
ligands has been superseded), as in [Co(Cl)2(NH3)4] for tetraamminedichloridocobalt(III). 2–
This order is sometimes varied to clarify which ligand is involved in a reaction. Polyatomic
ligand formulas are sometimes written in an unfamiliar sequence (as for OH2 in [Fe(OH2)6]2
for hexaaquairon(II)) to place the donor atom adjacent to the metal atom and so help to 104°
make the structure of the complex clear. The donor atom of an ambidentate ligand is some-
times indicated by underlining it, for example [Fe(OH2)5(NCS)]2. Note that, somewhat con-
Re
fusingly, the ligands in the formula are in alphabetical order of binding element, and thus
the formula and name of the complex may differ in the order in which the ligands appear.
Cl

E X A MPL E 7.1 Naming complexes

[R 2Cl8]22–
11 [Re
Name the complexes (a) [Pt(Cl)2(NH3)4]2; (b) [Ni(CO)3(py)]; (c) [Cr(edta)]
; (d) [Co(Cl)2(en)2];
(e) [Rh(CO)2I2]
.
NH3 4+
Answer To name a complex, we start by working out the oxidation number of the central metal atom and
then add the names of the ligands in alphabetical order. (a) The complex has two anionic ligands (Cl
),
four neutral ligands (NH3) and an overall charge of 2; hence the oxidation number of platinum must Co O
be 4. According to the alphabetical order rules, the name of the complex is tetraamminedichlorido-
platinum(IV). (b) The ligands CO and py (pyridine) are neutral, so the oxidation number of nickel must be
0. It follows that the name of the complex is tricarbonylpyridinenickel(0). (c) This complex contains the
hexadentate edta4
ion as the sole ligand. The four negative charges of the ligand result in a complex with
a single negative charge if the central metal ion is Cr3. The complex is therefore ethylenediaminetetra- 12 [(H3N)5CoOCo(NH3)5]4+
acetatochromate(III). (d) This complex contains two anionic chloride ligands and two neutral en ligands.
The overall charge of 1 must be the result of the cobalt having oxidation number 3. The complex
is therefore dichloridobis(ethylenediamine)cobalt(III). (e) This complex contains two anionic I
(iodido)
ligands and two neutral CO ligands. The overall charge of
1 must be the result of the rhodium having
oxidation number 1. The complex is therefore dicarbonyldiiodidorhodate(I).
Self-test 7.1 Write the formulas of the following complexes: (a) diaquadichlorido-platinum(II);
(b) diamminetetra(thiocyanato-N)chromate(III); (c) tris(ethylenediamine)rhodium(III); (d) bromidopenta-
carbonylmanganese(I); (e) chloridotris(triphenylphosphine)rhodium(I).

Constitution and geometry

Key points: The number of ligands in a complex depends on the size of the metal atom, the identity of
the ligands, and the electronic interactions.
The coordination number of a metal atom or ion is not always evident from the composi-
tion of the solid, as solvent molecules and species that are potentially ligands may simply
fill spaces within the structure and not have any direct bonds to the metal ion. For example,
X-ray diffraction shows that CoCl2.6H2O contains the neutral complex [Co(Cl)2(OH2)4]
and two uncoordinated H2O molecules occupying well-defined positions in the crystal.
Such additional solvent molecules are called solvent of crystallization.

1
When assigning oxidation numbers in carbonyl complexes, CO is ascribed a net oxidation number of 0.
World Journal of Chemical Education, 2017, Vol. 5, No. 5, 185-192
Available online at http://pubs.sciepub.com/wjce/5/5/8
©Science and Education Publishing
DOI:10.12691/wjce-5-5-8

Assessment of Greenness of Various Routes of Synthesis

of cis and trans Isomers of Bis(glycinato)copper(II)
Monohydrate: An Undergraduate
Chemistry Experiment
Ratul Biswas, Moumita Koley*

Undergraduate Programme, Indian Institute of Science, Bangalore, India

*Corresponding author: moumita@ug.iisc.in

Abstract Synthesis of cis and trans isomers of bis(glycinato)copper (II) monohydrate is a standard experiment
performed in undergraduate curriculum. Awareness on green chemistry on the other hand is also another important
topic for undergraduate students. The aim of this paper is to introduce these two important aspects through a unified
protocol, which was executed by an undergraduate student as summer project. The focus of this study is to present
the results of the evaluation of greenness of the synthetic routes traditionally used for the synthesis of cis/trans
copper gycinato complexes at undergraduate labs. The evaluation tables should help the educators to present an
overview of greenness of different preparative methodologies before the students. Each of the two geometrical
isomers had been prepared via two different routes available in literatures. The greenness had been assessed in
accordance with the 12 principles of Green Chemistry formulated by Paul Anastas and John Warner. A tabular form
of the Green Chemistry Mass Metrices is presented along with and other holistic graphic metrics such as the Green
Star and the Green Circle, the latter being based on the Globally Harmonized System (GHS) of Classification and
Labelling of Chemicals. Further, SWOT tables (Strengths, Weakness, Opportunities and Threats) have been
included to expose the upshots and drawbacks of the different synthetic routes.
Keywords: green chemistry, coordination compounds, synthesis, stereochemistry
Cite This Article: Ratul Biswas, and Moumita Koley, “Assessment of Greenness of Various Routes of
Synthesis of cis and trans Isomers of Bis(glycinato)copper(II) Monohydrate: An Undergraduate Chemistry
Experiment.” World Journal of Chemical Education, vol. 5, no. 5 (2017): 185-192. doi: 10.12691/wjce-5-5-8.

different synthetic routes and to determine the greenest

route. [14,15,16] Construction of the Green Star and the
1. Introduction Green Circle were achieved through the Globally
Harmonized System of Classification and Labelling of
Green Chemistry is a very important field of study. The Chemicals. Green star and Green Circle, both can provide
major goal of green chemistry, is the sustainable visual insight into the greenness of the various synthetic
development and production of chemicals by minimizing routes. [17,18] This is an instrumental tool in the
the use of hazardous substances, which poses higher risk undergraduate courses [19] not only as an exercise in the
towards environment. [1] With increasing focus on the laboratory, but also to install the feeling of concern about
environmental impact of chemical substances, it is the hazards of traditional processes and to align the
important to study the greenness of the synthetic routes of students towards the advantages of green and safe
various compounds that are important in our daily life. chemistry. [20,21]
[2,3,4,5] Even though the 12 principles of Green Copper serves as an essential element in our life cycle
Chemistry, formulated by Anastas and Warner, are well [22] and metabolism of copper in living organisms is
known today [6], the scrutiny of a synthetic route for definitely needed to be understood. In an effort to
greenness is still very complex and impractical. To understand the mechanism of metabolism of copper in
overcome this hurdle, the applications of a universal set of living systems, many copper amino-acid complexes have
green matrices to evaluate material efficiencies of been extensively studied as prototypes. [23,24] Moreover the
chemical transforms, is already well known. [7,8,9,10] study of Cu-glycenato complexes serves as an example of
Such metrices had already been in use by many research geometrical isomerism in coordination compounds. These
groups for accessing the relative performances of multiple complexes also can be used for introduction of the concept
routes for a specific target molecule. [11,12,13] In our group theory and symmetry elements present in molecules
present study, aid of simple Green Chemistry Mass to the undergraduate students. Therefore, preparation of
Metrics had been taken, for the evaluation of greenness of cis/trans (glycenato)copper(II)monohydrate complexes had
 World Journal of Chemical Education 186

traditionally been included in undergraduate curriculum for chemicals and solvents were purchased from SDfine
decades. In this era, where green chemistry teaching, is chemicals and used without further purification. IR and UV
very important, while choosing the methods for preparation spectra were recorded in Brucker ALPHA Platinum
of cis/trans Cu-glycenato complexes, it is worthwhile to ATR FTIR spectrophotometer (direct measurment without
look into perspective of greenness of different preparative KBr palate) and Libra BioChrom UV spectrophotometer
routs. The data for evaluation of greenness of different instrument respectively. Following 4 protocols had been
protocols were accomplished using the data obtained by used for the preparation of cis and trans isomers.
preparation of the complexes using the common methods
available in literatures. 2.1.1. Protocol 1A: Preparation of
cis-bis(glycenato)copper(II)monohydrate
from Copper Acetate Monohydrate [25]
2. Discussions on Synthetic Methodology Copper acetate monohydrate (2g, 10 mmol) was
dissolved in 15 mL of hot distilled water (around 70°C). A
In our present study, we had dealt with the preparation hot solution of ethanol (25 mL) was added to it. Gylcine
of copper salts of the simplest amino acid, glycine, which (1.5g, 20mmol), previously dissolved in 10 mL hot water
is well known experiment in undergraduate study. Copper (around 70°C), was added to this solution and stirred,
bisglycinate monohydrate is a blue compound which can maintaining the same temperature. Overheating of the
exists as two geometrical isomers, the cis and the trans solution was prohibited. After around 5 minutes of stirring,
copper glycinate monohydrate. the solution was cooled in an ice bath to form needle-like
Glycine, when deprotoned (as glycinate ion, NH2CH2COO-, precipitate. The precipitate was filtered and washed with
abbreviated as gly), is capable of forming two coordination small portions of ethanol (3 to 4 portions of 3 mL each)
bonds to the central metal ion (in this case copper(II)), and dried under vacuum and then air-dried for an hour.
through the nitrogen and oxygen atoms. Hence, it
functions as a chelating bidentate ligand and favors the 2.1.2. Protocol 1B: Preparation of cis-bis(gylcinato)
formation of bis(glycinato)copper(II) complex. In the copper(II)monohydrate from Copper Sulfate
reaction between copper(II) acetate monohydrate and Pentahydrate: [26]
glycine, the dissociation of glycine molecule produces Copper sulfate pentahydrate (1g, 4 mmol) was dissolved
glycinate anion, NH2CH2COO-(gly), which is a bidentate in 8.5 mL of 1M HCl at room temperature and glycine
ligand and easily replaces the monodentate acetate ion, powder (0.7g, 9.3 mmol) was slowly added while stirring.
CH3COO- in the copper complex. The dissociated proton The solution was then kept in a water bath and its temperature
from glycintate ion is accepted by the acetate ion and was maintained at around 55°C. After 30 minutes of
hence acetic acid is produced in the reaction between heating, about 1.5 – 2g of NaHCO3 was added slowly to
copper(II) acetate monohydrate and glycine. the solution until a blue precipitate was formed. The
precipitate was washed with small portions of ethanol (3
to 4 portions of 3 mL each) and dried under vacuum and
in an oven at 80°C for 10 minutes.
Scheme 1. 2.1.3. Protocol 2A: Preparation of Trans-bis(glycenato)
However, both the isomers exist as an equilibrium copper(II) Monohydrate from the cis Isomer [25]
mixture. But in an ethanolic solution at around 70oC, the To a 20 ml portion of the filtrate obtained from Protocol
cis isomer precipitates much quicker compared to the 1A was added 3g (15 mmol) of the cis isomer (previously
trans isomer, and hence leading to a shift in equilibrium prepared and dried) along with 2g (26.7 mmol) of glycine
away from trans, with producing only cis isomer. Cis powder. The solution was then refluxed at around 90°C
isomer is the kinetically favored product whereas trans for 1h. (An alternative method of preparation of the trans
isomer is thermodynamically more stable. The trans product would be to reflux the solution obtained in
isomer can be produced by converting the cis isomer by Protocol 1A prior to the filtration step at 90-100°C for 1h.)
supplying heat energy at 180°C for time of 15 minutes. The mixture, after reflux, was allowed to cool to room
Solid phase synthesis of the trans isomer was also reported. temperature and then filtered with frequent washes with
Another method for synthesis of the cis product from small portions (3 to 4 portions of 3 mL each) of ethanol.
copper sulphate pentahydrate was also evaluated. IR and
UV spectroscopy had been used for identification purpose 2.1.4. Protocol 2B: Preparation of Trans-bis(glycenato)
and also to distinguish the cis- and trans- isomers of copper(II)monohydrate in the Solid Phase from
Cu(gly)2.H2O. Copper Acetate Monohydrate: [27]
A mixture of 2g (10 mmol) of copper acetate
2.1. Preparation of Complexes monohydrate and 2g (26.6 mmol) of glycine powder was
ground using a mortar and pestle. The color of the mixture
Following section, enlists in brief, the procedure soon changed from green to pale blue. In about 1h, all the
concerning the synthesis of cis and trans copper glycinato reactants were exhausted. The powder was then transferred to
complexes. Syntheses had been performed in accordance a watch glass and left for 2h. The completion of the
with available literature protocols [25]. Note that all the reaction was indicated by a change of colour to pale blue.
main reagents were taken in stoichiometric amount Small portions of ethanol (3 to 4 portions of 3 mL each)
excepting the solvents, and other auxiliary substances and ether (2 portions of 2 mL each) were used to wash the
were taken in excess in Protocols 1A and 1B. All the sample. After washing, the product was dried in vacuum.
Descriptive
Inorganic Chemistry
FIFTH EDITION

Geoff Rayner-Canham
Sir Wilfred Grenfell College
Memorial University

Tina Overton
University of Hull

W. H. FREEMAN AND COMPANY

NEW YORK
Publisher: Clancy Marshall
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CHAPTER 19
Transition Metal Complexes

An obvious feature of the transition metals is the enormous number of

compounds. We will see the ways in which transition metals can form this galaxy
of compounds, introduce the naming system used for them, and discuss the
modern theories of bonding that are used to explain their diversity. In addition,
we will revisit hard-soft acid-base concepts in the context of transition metal
19.1 Transition Metals
compounds.
19.2 Introduction to Transition
Metal Complexes

T he transition metals have always held a special interest for inorganic

chemists. Whereas the compounds of the main group metals are
almost always white, the transition metal compounds come in every color
19.3 Stereochemistries
19.4 Isomerism in Transition Metal
Complexes
of the rainbow. Chemists were fascinated by the fact that it was some-
Platinum Complexes and Cancer
times possible to make compounds of the same formula but in different Treatment
colors. For example, chromium(III) chloride hexahydrate, CrCl3?6H2O,
19.5 Naming Transition Metal
can be synthesized in purple, pale green, and dark green forms.
Complexes
The initial explanation for this variety was that, like organic com-
pounds, the components of the transition metal compounds were 19.6 An Overview of Bonding
strung out in chains. It was the Swiss chemist Alfred Werner who, dur- Theories of Transition Metal
ing a restless night in 1893, proposed that the metal ion was central Compounds
and surrounded by the other ions and molecules. This novel theory 19.7 Crystal Field Theory
was accepted in Germany, but it received a hostile reception in the 19.8 Successes of Crystal Field
English-speaking world. Theory
Over the next eight years, Werner and his students prepared sev-
The Earth and Crystal Structures
eral series of transition metal compounds, searching for proof of his
theory. As more and more evidence accumulated, the opposition disin- 19.9 More on Electronic Spectra
tegrated, and he was awarded the Nobel Prize in Chemistry in 1913 in 19.10 Ligand Field Theory
recognition of his contribution. Although Werner deserved the credit 19.11 Thermodynamic versus
for devising this theory, we must always keep in mind that the toil at Kinetic Factors
the research bench was done mainly by his research students. In par-
19.12 Synthesis of Coordination
ticular, one of the most crucial pieces of evidence was established by a
Compounds
young British student, Edith Humphrey.
19.13 Coordination Complexes and
the HSAB Concept
19.1 Transition Metals 19.14 Biological Aspects

Although some people use the terms d-block elements and transition
metals interchangeably, this is not strictly correct. Inorganic chemists
generally restrict the term transition metal to an element that has at

499
500 CHAPTER 19 • Transition Metal Complexes

least one simple ion with an incomplete outer set of d electrons. For example,
chromium has two common oxidation states (plus several other less common
ones). The 13 oxidation state has a partially filled d set even though the 16 state
has an empty d set. Thus, chromium is considered to be a transition metal.

Atom Electron configuration Ion Electron configuration

Cr [Ar]4s13d5 Cr31 [Ar]3d3

Cr61 [Ar]

On the other hand, the only common oxidation state of scandium is 13.
Because this state has an empty d set, scandium (and the other members of
Group 3) is excluded from the transition metal designation. In fact, as we men-
tioned in Chapter 9, Section 9.5, scandium closely resembles the main group
metal aluminum in its chemical behavior. The Group 3 elements also resemble
the 4f-block elements in their chemistry and hence are discussed together with
them in Chapter 24.

Atom Electron configuration Ion Electron configuration

Sc [Ar]4s23d1 Sc31 [Ar]

At the other end of the d block, we have to consider the elements that
retain a full d set in their oxidation states. The Group 12 elements—zinc, cad-
mium, and mercury—fit this category. Their common oxidation state is 12.
Thus, these elements are not considered as transition metals. For this reason,
the Group 12 elements are covered in a separate chapter—Chapter 22.

Atom Electron configuration Ion Electron configuration

Zn [Ar]4s23d10 Zn21 [Ar]3d10

The elements from rutherfordium (element 104) to roentgenium (ele-

ment 111) are also transition metals. However, because they are all short-lived
radioactive elements, it is common to discuss them together with the actinoid
metals (see Chapter 24). To summarize, the elements commonly considered as
transition metals are shown in Figure 19.1.

19.2 Introduction to Transition Metal Complexes

We rarely encounter a “naked” transition metal ion, because the ion is usually
covalently bonded to other ions or molecules. These groupings are called metal
complexes, and it is the number and diversity of the metal complexes that pro-
vide the wealth of transition metal chemistry.
It was Alfred Werner’s proposal that metal ions had not only a particular value
of charge but also some characteristic “combining power.” That is, there is a
specific number of molecules or ions with which a transition metal will combine.
 19.2 Introduction to Transition Metal Complexes 501

H He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Lr Rf Db Sg Bh Hs Mt Ds Rg Uub Uut Uuq Uup Uuh Uuo

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No

FIGURE 19.1 A periodic table with the elements usually defined as transition metals,
shown in dark blue, and corresponding postactinoid transition metals, in light blue.

We now refer to this number (or numbers) as the coordination number(s) of

the metal ion, and it is usually 4 or 6. The molecules or ions that are covalently
bonded to the central metal ion are called ligands.
One of the best illustrations of the concept is shown by the series of com-
pounds that can be prepared from platinum(II) and ammonia, chloride ions,
and potassium ions. These compounds are shown in Table 19.1. The key to un-
derstanding this multiplicity of compounds was provided by measurements of
the electrical conductivity of their solutions and by gravimetric analysis using
silver nitrate solution. Thus, the presence of three ions in solution and 2 moles
of precipitating silver chloride in the first case can only be explained if the
two chloride ions are not covalently bonded to the platinum. In the second
complex, the presence of two ions and only 1 mole of free chloride ion that can
be precipitated as silver chloride shows that only one chloride ion is ionic and
that the other must be part of the coordination sphere of the platinum. Similar
arguments can be made for the other compounds.

TABLE 19.1 Formulas and structures of a series of platinum(II) complexes

Composition Number of ions Modern formulation

PtCl2?4NH3 3 [Pt(NH3)4]Cl2
PtCl2?3NH3 2 [PtCl(NH3)3]Cl
PtCl2?2NH3 0 [PtCl2(NH3)2] (two forms)
KPtCl3?NH3 2 K[PtCl3(NH3)]
K2PtCl4 3 K2[PtCl4]

The bonding theories will be introduced in Section 19.6, but for the moment we
can consider complex formation to be the result of coordinate covalent bond for-
mation, the metal ion acting as a Lewis acid and the ligands acting as Lewis bases.
502 CHAPTER 19 • Transition Metal Complexes

19.3 Stereochemistries

Transition metal complexes have a wide range of shapes. With four ligands,
there are two alternatives: tetrahedral and square planar. Tetrahedra are more
common in Period 4 transition metals, and square planar complexes are more
prevalent among Periods 5 and 6. Figure 19.2a shows the tetrahedral geom-
etry of the tetrachlorocobaltate(II) ion, [CoCl4]22, and Figure 19.2b shows the
square planar configuration of the tetrachloroplatinate(II) ion, [PtCl4]22.
There are few simple complexes with five ligands, but it is interesting to
find that, like the four-ligand situation, these complexes have two stereochem-
istries: trigonal bipyramidal, like the main group compounds, and square-based
pyramidal (Figure 19.3). The energy difference between these two configura-
tions must be very small, because the pentachlorocuprate(II) ion, [CuCl5]32,
adopts both structures in the solid phase, the preference depending on the
identity of the cation.

2% 3% 3%
Cl Cl Cl
2%
90 °
Co Cl
Cl Cl Cl Cu Cl Cl
Pt Cu
Cl Cl
Cl Cl 120 ° Cl Cl Cl
Cl 90 ° 90 °
109 12 °
Cl
(a) (b)
(a) (b)
FIGURE 19.2 (a) The tetrahedral
FIGURE 19.3 The two stereochemical
tetrachlorocobaltate(II) ion and (b) the square
arrangements of the pentachlorocuprate(II) ion:
planar tetrachloroplatinate(II) ion.
(a) trigonal bipyramid and (b) square-based
pyramid.

The most common number of simple ligands is six, and almost all of these
2%
F complexes adopt the octahedral arrangement. This configuration is shown in
F
90 °
F Figure 19.4 for the hexafluorocobaltate(IV) ion, [CoF6]22. Cobalt compounds
Co usually have cobalt oxidation states of 12 and 13; thus, as we discussed in
F F
Chapter 17, Section 17.2, it is fluoride that has to be used to attain the unusual
F
higher oxidation state of 14.
FIGURE 19.4 The octahedral
hexafluorocobaltate(IV) ion. Ligands
As mentioned earlier, the atoms, molecules, or ions attached to the metal ion
are called ligands. For most ligands, such as water or chloride ion, each occu-
pies one coordination site. These species are known as monodentate ligands
(from the Greek word meaning “one-toothed”).
There are several molecules and ions that take up two bonding sites; common
examples are the 1,2-diaminoethane molecule, H2NCH2CH2NH2 (commonly
called ethylenediamine and abbreviated “en”), and the oxalate ion, 2O2CCO22.
Such groups are called bidentate ligands (Figure 19.5).
 19.4 Isomerism in Transition Metal Complexes 503

O O FIGURE 19.5 (a) The 1,2-

H2C CH 2 C C diaminoethane molecule,
H2NCH2CH2NH2, and (b) the
H2N NH 2 %
O O% oxalate ion, 2O2CCO22. The atoms
that coordinate to the metal have
M M dashed lines to the metal ion, M,
(a) (b) showing how the bonding will
occur.

More complex ligands can be synthesized and will bond to three, four,
five, and even six coordination sites. These species are called tridentate,
%
tetradentate, pentadentate, and hexadentate ligands, respectively. The OOC COO%
best-known hexadentate ligand is the ethylenediaminetetraacetate ion, N N
%
22
(OOC)2NCH2CH2N(COO)222, abbreviated to (edta)42 (Figure 19.6). OOC COO%
All ligands that form more than one attachment to a metal ion are called FIGURE 19.6 The structure of
chelating ligands (from the Greek chelos, meaning “clawlike”). ethylenediaminetetraacetate ion.

Ligands and Oxidation States of Transition Metals

Another feature common to transition metals is their wide range of oxidation
states. The preferred oxidation state is very dependent on the nature of the ligand;
that is, various types of ligands stabilize low, normal, or high oxidation states.
1. Ligands that tend to stabilize low oxidation states. The two common ligands
that particularly favor metals in low oxidation states are the carbon monoxide
molecule and the isoelectronic cyanide ion. For example, iron has an oxidation
state of 0 in [Fe(CO)5].
2. Ligands that tend to stabilize “normal” oxidation states. Most common ligands,
such as water, ammonia, and halide ions, fall into this category. For example, iron
exhibits its common oxidation states of 12 and 13 with water: [Fe(OH2)6]21 and
[Fe(OH2)6]31. There are many cyanide complexes in normal oxidation states as
well. This is not unexpected, for the ion is a pseudo-halide ion (as discussed in
Chapter 17, Section 17.12) and hence is capable of behaving like a halide ion.
3. Ligands that tend to stabilize high oxidation states. Like nonmetals, tran-
sition metals only adopt high oxidation states when complexed with fluoride
and oxide ions. We have already mentioned the hexafluorocobaltate(IV) ion,
[CoF6]22, as one example. In the tetraoxoferrate(VI) ion, [FeO4]22, the oxide
ions stabilize the abnormal 16 oxidation state of iron.

19.4 Isomerism in Transition Metal Complexes

In the early history of coordination chemistry, the existence of pairs of com-

pounds with the same formula yet different properties proved to be very
perplexing to inorganic chemists. Werner was among the first to realize that
the different properties represented different structural arrangements (isomers).
Isomers can be categorized as structural isomers and stereoisomers. For
stereoisomers, the bonds to the metal ion are identical, whereas the bonds of
504 CHAPTER 19 • Transition Metal Complexes

FIGURE 19.7 Isomer types. Coordination

Compounds

Structural isomers Stereoisomers

(different bonds) (identical bonds)

Linkage Ionization Hydration Coordination Geometric Optical

isomers isomers isomers isomers isomers isomers

structural isomers are different. These categories can be further subdivided, as

shown in Figure 19.7.

Structural Isomerism
Structural isomerism has four common types: linkage isomerism, ionization
isomerism, hydration isomerism, and coordination isomerism. Ionization and hy-
dration isomerism are sometimes categorized together as coordination-sphere
isomerism because in both cases it is the identity of the ligands that differs.
1. Linkage isomerism. Some ligands can form bonds through more than one
atom. For example, the thiocyanate ion, NCS2, can bond through either the ni-
trogen or the sulfur. This particular ambidentate ligand is a borderline base (see
Chapter 7, Section 7.7) since the choice of ligating atom depends in part on the
hard-soft acid nature of the metal ion. A classic example of linkage isomerism
involves the nitrite ion, which can form bonds through the nitrogen atom, 2NO2,
referred to as nitro, or through one of the oxygen atoms, 2ONO, referred to as
nitrito. A pentamminecobalt(III) complex, Co(NH3)5Cl2(NO2), conveniently
illustrates this isomerism since the two isomers have different colors. One of
these, the red form, contains the [Co(ONO)(NH3)5]21 ion, in which one of the
oxygen atoms of the nitrite ion is bonded to the cobalt(III) ion (Figure 19.8a).
The other isomer, the yellow form, contains the [Co(NO2)(NH3)5]21 ion, in
which the nitrogen atom is bonded to the cobalt(III) ion (Figure 19.8b).

FIGURE 19.8 The two 2!

O
linkage isomers of the
pentamminecobalt(III) nitrite N 2!
complex: (a) the nitrito form, O O
(b) the nitro form. O N

H3N NH3 H3N NH3

Co Co
H3N NH3 H 3N NH3

NH3 NH3

(a) (b)
Black plate (3,1)
 Black plate (4,1)

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 Black plate (536,1)

536 Chapter 19 . d-Block chemistry: general considerations

Fig. 19.1 Trends in metallic radii (rmetal ) across the three rows of s- and d-block metals K to Zn, Rb to Cd, and Cs to Hg.

. metals of the second and third rows are sometimes called like atoms and, therefore, the discussion is extremely
the heavier d-block metals; approximate.
. Ru, Os, Rh, Ir, Pd and Pt are collectively known as the
platinum-group metals.

Electronic configurations 19.3 Physical properties

To a first approximation, the observed ground state electro-
nic configurations of the first, second and third row d-block In this section, we consider physical properties of the d-block
metal atoms correspond to the progressive filling of the 3d, metals (see cross references in Section 19.1 for further
4d and 5d atomic orbitals respectively (Table 1.3). However, details); an extended discussion of properties of the heavier
there are minor deviations from this pattern, e.g. in the first metals is given in Section 22.1. Nearly all the d-block
row, the ground state of chromium is [Ar]4s1 3d 5 rather than metals are hard, ductile and malleable, with high electrical
[Ar]4s2 3d 4 . The reasons for these deviations are beyond the and thermal conductivities. With the exceptions of Mn, Zn,
scope of this book: we should need to know both the Cd and Hg, at room temperature, the metals possess one
energy difference between the 3d and 4s atomic orbitals of the typical metal structures (see Table 5.2). The metallic
when the nuclear charge is 24 (the atomic number of Cr) radii (rmetal ) for 12-coordination (Table 5.2 and Figure 19.1)
and the interelectronic interaction energies for each of the are much smaller that those of the s-block metals of
[Ar]4s1 3d 5 and [Ar]4s2 3d 4 configurations. Fortunately, comparable atomic number; Figure 19.1 also illustrates that
M2þ and M3þ ions of the first row d-block metals all have values of rmetal :
electronic configurations of the general form [Ar]3d n , and
. show little variation across a given row of the d-block;
so the comparative chemistry of these metals is largely
. are greater for second and third row metals than for first
concerned with the consequences of the successive filling of
row metals:
the 3d orbitals. For metals of the second and third rows,
. are similar for the second and third row metals in a given
the picture is more complicated, and a systematic treatment
triad.
of their chemistry cannot be given. The emphasis in this and
the next chapter is therefore on the first row metals, but we This last observation is due to the so-called lanthanoid con-
shall include some material that illustrates ways in which traction (the steady decrease in size along the 14 lanthanoid
the heavier metals differ from their lighter congeners. metals between La and Hf; see Section 24.3).
An important point that must not be forgotten is that d- Metals of the d-block are (with the exception of the group
block metal atoms are, of course, many-electron species, 12 metals) much harder and less volatile than those of the s-
and when we discuss, for example, radial distribution block. The trends in enthalpies of atomization (Table 5.2)
functions of the nd atomic orbitals, we refer to hydrogen- are shown in Figure 19.2. Metals in the second and third
 Black plate (548,1)

548 Chapter 19 . d-Block chemistry: general considerations

Fig. 19.9 (a) The structure of ½HfðBH4 Þ4  determined by

neutron diffraction at low temperature [R.W. Broach et
al. (1983) Inorg. Chem., vol. 22, p. 1081]. Colour code: Hf,
red; B, blue; H, white. (b) The 12-vertex cubeoctahedral Fig. 19.10 Classification of types of isomerism in metal
coordination sphere of the Hf(IV) centre in ½HfðBH4 Þ4 . complexes.

cis-isomers, e.g. trans-½CaI2 ðTHFÞ4  (Section 11.5) and the

The isomers are also easily distinguished by IR spectroscopy;
trans- and cis-isomers of N2 F2 (Section 14.7). These are geo-
free and coordinated sulfate ions give rise to one or three IR
metrical isomers, and our previous discussion of this topic
active S
O stretching vibrations respectively.
(see Section 1.20) will not be elaborated further here.
½NH4 Br; NH3 ; O2
CoBr2












½CoðNH3 Þ5 ðH2 OÞBr3
"

Self-study exercises

"
All the answers can be found by reading Section 1.20.
½CoðNH3 Þ5 BrBr2
1. Draw possible structures for the square planar complexes

[PtBr2 (py)2 ] and [PtCl3 (PEt3 )]
and give names to distinguish Ag2 SO4
between any isomers that you have drawn.
"
2. In [Ru(CO)4 (PPh3 )], the Ru centre is in a trigonal bipyramidal ½CoðNH3 Þ5 Br½SO4  ð19:6Þ
environment. Draw the structures of possible isomers and give
names to distinguish between them. conc H2 SO4
½CoðNH3 Þ5 BrBr2








½CoðNH3 Þ5 ðSO4 Þ½HSO4 
"

3. Draw the structures and name the isomers of octahedral

[CrCl2 (NH3 )4 ]þ . BaBr2

"

4. Octahedral [RhCl3 (H2 O)3 ] has two isomers. Draw their

structures and give them distinguishing names. ½CoðNH3 Þ5 ðSO4 ÞBr ð19:7Þ

In this section, we shall be concerned with other types of Structural isomerism: hydration isomers
isomerism exhibited by d-block metal complexes, and we
use a classification that goes back to the work of Werner Hydration isomers result from the interchange of H2 O and
(Figure 19.10). another ligand between the first coordination sphere and the
ligands outside it.
Structural isomerism: ionization isomers The classic example of hydrate isomerism is that of the
Ionization isomers result from the interchange of an anionic compound of formula CrCl3 6H2 O. Green crystals of
ligand within the first coordination sphere with an anion chromium(III) chloride formed from a hot solution obtained
outside the coordination sphere. by reducing chromium(VI) oxide with concentrated hydro-
chloric acid are ½CrðH2 OÞ4 Cl2 Cl2H2 O. When this is dis-
Examples of ionization isomers are violet ½CoðNH3 Þ5 Br½SO4  solved in water, the chloride ions in the complex are slowly
(prepared by reaction scheme 19.6) and red replaced by water to give blue-green ½CrðH2 OÞ5 ClCl2 H2 O
½CoðNH3 Þ5 ðSO4 ÞBr (prepared by reaction sequence 19.7). and finally violet ½CrðH2 OÞ6 Cl3 . The complexes can be
These isomers can be readily distinguished by appropriate distinguished by precipitation of the free chloride ion using
qualitative tests for ionic sulfate or bromide, respectively. aqueous silver nitrate.
 Black plate (549,1)

Chapter 19 . Isomerism in d-block metal complexes 549

Structural isomerism: coordination Polymerization isomers denote complexes which have the
isomerism same empirical formulae but different molecular masses.

Coordination isomers are possible only for salts in which Examples of polymerization isomers are:
both cation and anion are complex ions; the isomers
arise from interchange of ligands between the two metal . ½PtCl2 ðNH3 Þ2  and ½PtðNH3 Þ4 ½PtCl4 ;
centres. . ½CoðNH3 Þ3 ðNO2 Þ3  and ½CoðNH3 Þ6 ½CoðNO2 Þ6 .

Examples of coordination isomers are: Stereoisomerism: geometrical isomers

. ½CoðNH3 Þ6 ½CrðCNÞ6  and ½CrðNH3 Þ6 ½CoðCNÞ6 ;
Distinguishing between cis- and trans-isomers of a square
. ½CoðNH3 Þ6 ½CoðNO2 Þ6  and
planar complex or between mer- and fac-isomers of an
½CoðNH3 Þ4 ðNO2 Þ2 ½CoðNH3 Þ2 ðNO2 Þ4 ;
octahedral complex is most unambiguously confirmed by
. ½PtII ðNH3 Þ4 ½PtIV Cl6  and ½PtIV ðNH3 Þ4 Cl2 ½PtII Cl4 .
structural determinations using single-crystal X-ray diffrac-
tion. Vibrational spectroscopy (applications of which were
Structural isomerism: linkage isomerism introduced in Section 3.7) may also be of assistance. For
Linkage isomers may arise when one or more of the ligands example, Figure 19.11 illustrates that the asymmetric stretch
can coordinate to the metal ion in more than one way, e.g. in for the PtCl2 unit in ½PtðNH3 Þ2 Cl2  is IR active for both the
[SCN]
(19.16), both the N and S atoms are potential donor trans- and cis-isomers, but the symmetric stretch is IR active
sites. only for the cis-isomer. In square planar complexes con-
taining phosphine ligands, the 31 P NMR spectrum may be
–
particularly diagnostic, as is illustrated in Box 19.1.
S C N The existence of ions or molecules in different structures
(19.16) (e.g. trigonal bipyramidal and square-based pyramidal
½NiðCNÞ5 3
Þ is just a special case of geometrical isomerism.
Thus, the complex ½CoðNH3 Þ5 ðNCSÞ2þ has two isomers In the cases of, for example, tetrahedral and square planar
which are distinguished by using the following nomen- ½NiBr2 ðPBzPh2 Þ2  (Bz ¼ benzyl), the two forms can be dis-
clature: tinguished by the fact that they exhibit different magnetic
. in ½CoðNH3 Þ5 ðNCS-NÞ2þ , the thiocyanate ligand co- properties as we shall discuss in Section 20.8. To complicate
ordinates through the nitrogen donor atom; matters, square planar ½NiBr2 ðPBzPh2 Þ2  may exist as either
. in ½CoðNH3 Þ5 ðNCS-SÞ2þ , the thiocyanate ion is bonded trans- or cis-isomers.
to the metal centre through the sulfur atom.
Stereoisomerism: optical isomers
Scheme 19.8 shows how linkage isomers of
½CoðNH3 Þ5 ðNO2 Þ2þ can be prepared. Optical isomerism is concerned with chirality, and some
important terms relating to chiral complexes are defined in
dil NH3 ðaqÞ
½CoðNH3 Þ5 ClCl2








½CoðNH3 Þ5 ðH2 OÞCl3
"
Box 19.2. The simplest case of optical isomerism among
d-block complexes involves a metal ion surrounded by

NaNO2 NaNO2 ; conc HCl three didentate ligands, for example ½CrðacacÞ3  or
½CoðenÞ3 3þ (Figures 3.16b and 19.12). These are examples
"

"

warm HCl or of tris-chelate complexes. Pairs of enantiomers such as
-

spontaneous
½CoðNH3 Þ5 ðNO2 -OÞCl2




















3


½CoðNH3 Þ5 ðNO2 -NÞCl2
" and -½CrðacacÞ3  or
- and -½CoðenÞ3 Cl3 differ only in
red UV yellow their action on polarized light. However, for ionic com-
(19.8) plexes such as ½CoðenÞ3 3þ , there is the opportunity to
form salts with a chiral counter-ion A
. These salts now
In this example, the complexes ½CoðNH3 Þ5 ðNO2 -OÞ2þ and contain two different types of chirality: the
- or -
½CoðNH3 Þ5 ðNO2 -NÞ2þ can be distinguished by using IR chirality at the metal centre and the (þ) or (
) chirality
spectroscopy. For the O-bonded ligand, characteristic of the anion. Four combinations are possible of which
absorption bands at 1065 and 1470 cm
1 are observed, the pair f
-ðþÞg and f-ð
Þg is enantiomeric as is the
while for the N-bonded ligand, the corresponding vibrational pair f
-ð
Þg and f-ðþÞg. However, with a given
wavenumbers are 1310 and 1430 cm
1 . anion chirality, the pair of salts f
-ð
Þg and f-ð
Þg are
diastereomers (see Box 19.2) and may differ in the packing
Structural isomerism: polymerization of the ions in the solid state, and separation by fractional
crystallization is often possible.
isomerism
Bis-chelate octahedral complexes such as ½CoðenÞ2 Cl2 þ
‘Polymerization’ isomerism is a rather unfortunate term exist in both cis- and trans-isomers depending on the arrange-
since we are actually not dealing with polymeric structures. ment of the chloro ligands. In addition, the cis-isomer (but
 Black plate (551,1)

Chapter 19 . Isomerism in d-block metal complexes 551

CHEMICAL AND THEORETICAL BACKGROUND

Box 19.2 Definitions and notation for chiral complexes

Chirality was introduced in Section 3.8 and Box 3.2. Here,

we add to this introduction and collect together some terms
that are frequently encountered in discussing optically
active complexes.
Enantiomers are a pair of stereoisomers that are non-
superposable mirror images.
∆ Λ
Diastereomers are stereoisomers that are not enantiomers.
(þ) and (
) prefixes: the specific rotation (see Section 3.8)
of enantiomers is equal and opposite, and a useful means of
d and k prefixes: the situation with chelating ligands is
distinguishing between enantiomers is to denote the sign
often more complicated than the previous paragraph sug-
of ½D . Thus, if two enantiomers of a compound A have
gests. Consider the chelation of 1,2-diaminoethane to a
½D values of þ128 and
128, they are labelled (þ)-A and
metal centre. The 5-membered ring so formed is not planar
(
)-A.
but adopts an envelope conformation. This is most easily
d and l prefixes: sometimes (þ) and (
) are denoted by
seen by taking a Newman projection along the C
C bond
dextro- and laevo- (derived from the Latin for right and
of the ligand; two enantiomers are possible and are
left) and these refer to right- and left-handed rotation of
distinguished by the prefixes d and l.
the plane of polarized light respectively; dextro and laevo
are generally abbreviated to d and l.
The þ=
or d/l notation is not a direct descriptor of the
absolute configuration of an enantiomer (the arrangement
of the substituents or ligands) for which the following
prefixes are used.
R and S prefixes: the convention for labelling chiral carbon
atoms (tetrahedral with four different groups attached) uses
the Cahn–Ingold–Prelog notation. The four groups attached
to the chiral carbon atom are prioritized according to the
atomic number of the attached atoms, highest priority
being assigned to highest atomic number, and the molecule
then viewed down the C
X vector, where X has the lowest
priority. The R- and S-labels for the enantiomers refer to a P and M descriptors: a helical, propeller or screw-shaped
clockwise (rectus) and anticlockwise (sinister) sequence of structure (e.g. Sn has a helical chain) can be right- or left-
the prioritized atoms, working from high to low. Example: handed and is termed P (‘plus’) or M (‘minus’), respectively.
CHClBrI, view down the C
H bond: This is illustrated with (P)- and (M)-hexahelicene:

1 1 H H H H
I I
H H
H H H H
C C
Cl Br Br Cl
3 2 2 3

R S
(P)-hexahelicene (M)-hexahelicene

This notation is used for chiral organic ligands, and also for
tetrahedral complexes. For detailed information, see:

and  prefixes: enantiomers of octahedral complexes IUPAC: Nomenclature of Inorganic Chemistry (Recom-
containing three equivalent didentate ligands (tris-chelate mendations 1990), ed. G.J. Leigh, Blackwell Scientific
complexes) are among those which are distinguished using Publications, Oxford, p. 182.

(delta) and  (lambda) prefixes. The octahedron is Basic terminology of stereochemistry: IUPAC Recommenda-
viewed down a three-fold axis, and the chelates then define tions 1996 (1996) Pure and Applied Chemistry, vol. 68,
either a right- or left-handed helix. The enantiomer with p. 2193.
right-handedness is labelled
, and that with left-handedness A. von Zelewsky (1996) Stereochemistry of Coordination
is . Compounds, Wiley, Chichester.
J. Chem. Sci. (2018) 130:116 © Indian Academy of Sciences
https://doi.org/10.1007/s12039-018-1515-3
REGULAR ARTICLE

Geometric isomerism effect on catalytic activities of

bis(oxalato)diaquochromates(III) for 2-chloroallyl alcohol
oligomerization

JOANNA DRZEŻDŻON∗ , LECH CHMURZYŃSKI and DAGMARA JACEWICZ

Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, 80-308 Gdańsk, Poland
E-mail: joanna.drzezdzon@ug.edu.pl

MS received 17 May 2018; revised 29 June 2018; accepted 30 June 2018; published online 10 August 2018

Abstract. The cis- and trans-potassium bis(oxalato)diaquochromates(III) have been studied towards their
catalytic activity for the 2-chloroallyl alcohol oligomerization. The geometric isomerism effect on the
oligomerization products under mild reaction conditions has been investigated. The molecular masses and
tactic structures of obtained poly(2-chloroallyl alcohols) have been compared and analyzed. The mechanisms
of oligomerization processes have been proposed. It has been proven that two studied complexes – cis-
K[Cr(C2 O4 )2 (OH2 )2 ] and trans-K[Cr(C2 O4 )2 (OH2 )2 ]·3H2 O are highly active catalysts for the oligomerization
of the beta-olefin derivative.

Keywords. Chromium(III) complexes; catalytic activities; polymerization; oxalate ion.

1. Introduction information regarding the chromium(III) complexes

used in the polymerization of 2-chloroallyl alcohol (2
The products of olefin polymerization are used in -chloro-2-propen-1-ol). Recently, the catalytic prop-
industry for the production of various plastics, e.g. erties of the dipicolinate chromium(III) complexes
containers, household articles, orthopedic prostheses, with 2,2 -bipyridine and 4,4 -dimetoxy-2,2 -bipyridine
laboratory and medical devices. 1–3 The chromium(III) for the preparation of poly(2-chloroallyl alcohol) at
complexes are commonly used as catalysts to the olefin the atmospheric pressure and room temperature were
and its derivatives polymerization. 4,5 The catalytic activ- described. 7 These dicarboxylate chromium(III) com-
ity of the non-metallocene chromium(III) complexes for plexes exhibit very high catalytic activities, i.e. 2609.86
the olefin polymerization was discovered in the first half and 2254.57 g·mmol−1 ·h−1 for [Cr(dipic)2 ][Cr(bipy)
of the 1990s. 4 This kind of chromium(III) complexes (dipic)H2 O]·2H2 O and [Cr(dipic)2 ]Hdmbipy·2.5H2 O,
is the focus for the olefin polymerization researchers respectively. 7
because these catalysts are very active and stable in the The aim of the our studies described in this report is
industrial production of oligomers. 6,7 first of all to investigate the catalytic activities of dicar-
Poly(vinyl alcohol) (PVA) and its derivatives have boxylate chromium(III) complexes cis-K[Cr(C2 O4 )2
orthopedic applications. 8 PVA is used as a synthetic car- (OH2 )2 ] and trans-K[Cr(C2 O4 )2 (OH2 )2 ]·3H2 O for the
tilage. 8 Moreover, PVA and its derivatives are used in the 2-chloro-2-propen-1-ol oligomerization. Secondly, the
world production of adhesives, hydrogels and stabilizers geometric isomerism effect in the bis(oxalato)diaquoch-
for emulsions. 9,10 Besides PVA, polypropylene (PP) is romates(III) has been analyzed for the values of the
the material commonly used in the polymer industries, 11 catalytic activity of the synthesized complexes and the
such as, HVDC cable insulation. 12 The derivative of identity of the oligomerization products.
vinyl alcohol and propylene, i.e. 2-chloroallyl alcohol
is a monomer used for the production of polymeric
hydroxy compounds. The copolymers of 2-chloroallyl 2. Experimental
alcohol is used for the production of artificial glasses
and elastomers. 13–15 In the literature, there is little 2.1 Materials

All the reagents used in this work, potassium dichromate (99%

* For correspondence
purity), oxalic acid (99% purity), 2-chloro-2-propen-1-ol

1
116 Page 2 of 7 J. Chem. Sci. (2018) 130:116

(technical grade, 90% purity), modified methylaluminoxane 125.76 MHz) instrument (300 K): (1) poly(2-chloroallyl
(MMAO-12, 7 wt% aluminum in toluene), toluene (99% alcohols), cis-K[Cr(C2 O4 )2 (OH2 )2 ] with MMAO-12; (2)
purity), were purchased from Sigma-Aldrich. poly(2-chloroallyl alcohols), trans-K[Cr(C2 O4 )2 (OH2 )2 ]
· 3H2 O with MMAO-12. 1,1,2,2-Tetrachloroethane-D2
2.2 Synthesis of cis-K[Cr(C2 O4 )2 (OH2 )2 ] and (C2 D2 Cl4 ) was used as the solvent.
trans-K[Cr(C2 O4 )2 (OH2 )2 ]·3H2 O
2.5 Synthesis of poly(2-chloroallyl alcohols)
The cis-K[Cr(C2 O4 )2 (OH2 )2 ] and trans-K[Cr(C2 O4 )2
(OH2 )2 ]·3H2 O complexes were synthesized according to the The oligomerization processes were carried out under
method of Werner and his coworkers. 16,17 The composition constant conditions: at the atmospheric pressure, at 21 ◦ C,
and purity of the synthesized bis(oxalato)diaquochromates under the nitrogen atmosphere, continuous mixing using a
(III) complexes were confirmed by elemental analysis of car- magnetic stirrer. Cis-K[Cr(C2 O4 )2 (OH2 )2 ] (3 μmol,
bon and hydrogen using the CARLO ERBA type CHNS–O 0.84 mg) was dissolved in toluene (2 mL). This chromium(III)
1108 analyzer. Anal. Calcd. for trans-K[Cr(C2 O4 )2 (OH2 )2 ]· complex was used as a catalyst. The obtained solution was
3H2 O: C, 13.66; H, 2.85%; and for cis-K[Cr(C2 O4 )2 (OH2 )2 ] placed in the glass cell with a sealed stopper. Subsequently,
C, 15.91; H, 1.95%. Found for trans-K[Cr(C2 O4 )2 (OH2 )2 ]· 3 mL of the MMAO-12 solution were dropped in to the com-
3H2 O: C, 13.41; H, 2.82%, and for cis-K[Cr(C2 O4 )2 (OH2 )2 ]: plex solution in the glass cell. In the next step, 3 mL of
C, 15.19.; H, 1.80%. 2-chloro-2-propen-1-ol were added to the MMAO-12 and cis-
The crystallographic data for cis-K[Cr(C2 O4 )2 (OH2 )2 ] K[Cr(C2 O4 )2 (OH2 )2 ] mixture in the glass cell. After 20 min,
and trans-K[Cr(C2 O4 )2 (OH2 )2 ]·3H2 O have been described the oligomerization process was finished. The product of the
in the literature. 16,18 The physicochemical properties of oligomerization (2.17 g) has been studied by MALDI-TOF
cis-K[Cr(C2 O4 )2 (OH2 )2 ] and trans-K[Cr(C2 O4 )2 (OH2 )2 ] mass spectrometry and NMR spectroscopy.
·3H2 O have also been characterized earlier in the litera- The same oligomerization procedure was carried out
ture. 19 The TG–MS analysis confirmed the thermodynamic using trans-K[Cr(C2 O4 )2 (OH2 )2 ]·3H2 O (3 μmol, 1.00 mg)
stability of the synthesized isomers and it shows that the instead of cis-K[Cr(C2 O4 )2 (OH2 )2 ]. The product of the
trans-K[Cr(C2 O4 )2 (OH2 )2 ]·3H2 O is more stable in the solid oligomerization weighed 3.49 g.
state than cis-K[Cr(C2 O4 )2 (OH2 )2 ]. Moreover, both isomers
undergo dehydration and decarboxylation. 19
3. Results and Discussion
2.3 MS spectra
Two geometric isomers cis-K[Cr(C2 O4 )2 (OH2 )2 ] and
The positive-ion mode MALDI-TOF mass spectra of obtained
poly(2-chloroallyl alcohols) with the 2,5-dihydroybenzoic
trans-K[Cr(C2 O4 )2 (OH2 )2 ]·3H2 O (Figure 1) after reac-
acid (DHB) matrix were recorded on the Bruker Biflex III tion with MMAO-12 were used as the catalyst sys-
spectrometer. tems for the preparation of poly(2-chloroallyl alcohols).
Both the synthesized complexes contain two oxalate
2.4 NMR spectra [O− , O− ] ligands, however, with different positions in
space. In our studies, two processes of 2-chloro-2-
The 1 H and 13 C NMR spectra of the following mixtures propen-1-ol oligomerization have been conducted: in
were obtained using the Bruker Avance III 500 (500.13/ the first sample, the cis isomer was used as a catalyst,

Figure 1. (A) trans-K[Cr(C2 O4 )2 (OH2 )2 ]·3H2 O; (B) cis-K[Cr(C2 O4 )2 (OH2 )2 ].

 Jurnal Kimia Indonesia
Vol. 1 (1), 2006, h. 7-12

Sintesis Senyawa Kompleks K[Cr(C2O4)2(H2O)2].2H2O dan

[N(n-C4H9)4][CrFe(C2O4)3].H2O
Kiki Adi Kurnia,1 Djulia Onggo,1 Dave Patrick,2 K. L. Stevenson2
1
Kimia Fisik dan Anorganik, FMIPA ITB
Jl. Ganesha 10 Bandung 40132, Indonesia
2
Chemistry Department, Purdue University
Fort Wayne, Indiana 46805, Amerika Serikat
Email: djulia@chem.itb.ac.id

Abstrak. Senyawa kompleks K[Cr(C2O4)2(H2O)2].2H2O dan [N(n-C4H9)4][CrFe(C2O4)3].H2O telah

berhasil disintesis. Rumus kimia kedua senyawa tersebut ditentukan dari kadar ion-ion penyusunnya.
Ikatan ion oksalat pada ion logam telah diamati dari spektrum IR pada 520–490 cm–1 dan 460–405
cm–1 sedangkan puncak pada 1650–1610 cm–1 dan 810–780 cm–1 menunjukkan peran ion oksalat
sebagai ligan jembatan. Ligan oksalat pada senyawa kompleks terkoordinasi secara oktahedral. Ini
diamati dari spektrum elektronik pada daerah sinar tampak. Senyawa [N(n-C4H9)4][CrFe(C2O4)3].H2O
merupakan kompleks polimer yang ditandai dengan hantaran molar yang relatif kecil, sekitar 50-60
μS. Pada suhu ruang, kedua senyawa kompleks bersifat paramagnet. Momen magnet K[Cr(C2O4)2
(H2O)2].2H2O bernilai 3,8 BM sesuai dengan keberadaan tiga elektron tidak berpasangan pada ion
Cr(III). Pengukuran kerentanan magnet senyawa [N(n-C4H9)4][CrFe(C2O4)3].H2O pada rentang 1-300
K menunjukkan bahwa senyawa kompleks ini memiliki interaksi feromagnet, dengan tetapan Weiss
+ 4,31 dan suhu Curie, Tc, terjadi pada 25 K. Senyawa [N(n-C4H9)4][CrFe(C2O4)3].H2O memberikan
momen magnet maksimum 49 BM pada suhu 1 K.
Kata kunci: ligan oksalat, feromagnet, kompleks polimer, ligan jembatan, paramagnet.

Senyawa kompleks binuklir oksalat memiliki

Pendahuluan
struktur bervariasi yang terdiri dari jaringan ion-
Ion oksalat merupakan ligan yang istimewa ion logam bi- dan tri-valensi berkoordinasi dengan
karena mampu membentuk senyawa kompleks oksalat sebagai ligan jembatan membentuk
dengan berbagai ion logam transisi menghasilkan lapisan-lapisan berdimensi satu sampai tiga.
senyawa dengan sifat dan karakter yang bervariasi. Dengan struktur ini ion oksalat berperan sebagai
Ion oksalat memiliki empat atom donor namun mediator pertukaran sifat magnet di antara ion-ion
hanya dua atom yang menjadikannya sebagai ligan logam tersebut.
bidentat yang berikatan dengan ion logam
membentuk senyawa kompleks mono, bis dan tris
oksalat. Ion oksalat juga dapat berfungsi sebagai
ligan jembatan yang menghubungkan lebih dari
satu inti ion logam transisi, baik ion logam yang
sejenis maupun berbeda jenis sehingga membentuk
kompleks polimer berdimensi satu, dua, bahkan Gambar 1. Struktur ion oksalat
tiga.1 Senyawa kompleks oksalat dengan satu ion Senyawa kompleks binuklir-oksalat yang me-
pusat disebut senyawa kompleks mononuklir miliki sifat magnet unik adalah senyawa kompleks
oksalat dan senyawa kompleks dengan dua ion A[M(II)Cr(III)(C2O4)3 ] dengan A adalah kation
pusat, baik sama maupun berbeda, disebut senyawa N(n-C4H9)4]+, dan M(II) adalah ion logam Co, Ni,
kompleks binuklir oksalat. Struktur ion oksalat Mn, dan Fe. Senyawa kompleks tersebut bersifat
dapat dilihat pada Gambar 1. feromagnet dengan suhu Curie, Tc, berkisar antara
Senyawa kompleks mononuklir oksalat dengan 6 – 14 K.3 Penggantian ion krom(III) dengan ion
ion Cr3+ sebagai ion pusatnya menunjukkan sifat besi (III) membentuk kompleks
thermochromic, yaitu perubahan warna yang A[M(II)Fe(III)(C2O4)3] dengan M(II) adalah ion
disebabkan oleh suhu dan gugus optis aktif.2

Dapat dibaca di www.kimiawan.org/journal/jki

 Kiki Adi Kurnia, Djulia Onggo, Dave Patrick, K.L Stevenson

logam Ni dan Fe, ternyata menunjukkan sifat Hasil dan Pembahasan

ferimagnet dengan suhu Neel, TN, pada 28 K dan Sintesis K[Cr(C2O4)2(H2O)2].2H2O yang dilaku-
43 K.4 Jika M(II) yang digunakan pada senyawa kan melalui dua teknik sintesis yang berbeda
tersebut adalah ion mangan(II), ternyata perilaku ternyata menghasilkan dua padatan senyawa kom-
antiferimagnet teramati pada suhu sekitar 50 K. pleks yang berbeda. Pada metode yang pertama,
Sintesis kompleks mono dan bi-nuklir dengan dihasilkan padatan berwarna merah-ungu, sedang-
ligan oksalat dilakukan untuk mendapatkan infor- kan pada metode yang kedua dihasilkan padatan
masi keterkaitan struktur dan sifat magnet senyawa berwarna ungu. Padatan berwarna merah-ungu
kompleks yang terbentuk. relatif mudah terbentuk tetapi kelarutannya cukup
Percobaan tinggi dalam air sehingga rendeman yang diperoleh
hanya 68%. Sedangkan padatan berwarna ungu,
Sintesis K[Cr(C2O4)2(H2O)2].2H2O. Pada pe-
relatif sulit terbentuk dan kelarutannya juga cukup
nelitian ini, dilakukan dua teknik sintesis senyawa
tinggi dalam air dan rendemen yang diperoleh
kompleks K[Cr(C2O4)2(H2O)2].2H2O. Pada meto-
berkisar 64%. Hasil analisis unsur dan gugus pe-
de yang pertama, sebanyak 4 gram kalium
nyusun kedua senyawa ini tidak menunjukkan
dikromat dilarutkan dalam 5 mL air mendidih.
perbedaan yang berarti, kedua senyawa tersebut
Setelah larut sempurna, ke dalam larutan ini
memiliki rumus kimia yang sama dan keduanya
ditambahkan larutan 12 gram asam oksalat dihidrat
merupakan senyawa kompleks mononuklir.
dalam 10 mL air mendidih. Larutan didinginkan
Senyawa kompleks binuklir yang telah di-
perlahan hingga terbentuk padatan. Padatan yang
sintesis berupa serbuk berwarna kuning keemasan,
terbentuk disaring dengan menggunakan kaca
dengan rumus kimia [N(n-C4H9)4][CrFe(C2O4)3].
masir dan dicuci menggunakan etanol dingin.
H2O yang dihitung atas dasar hasil analisis ion dan
Kemudian padatan dikeringkan dalam desikator.
gugus pendukungnya. Sintesis senyawa ini relatif
Metode kedua dilakukan dengan jumlah bahan
lebih sulit dilakukan dibandingkan sintesis
yang sama namun prosedur sintesis berbeda. Asam
senyawa kompleks oksalat mononuklir. Waktu
oksalat dihidrat dan kalium dikromat, keduanya
yang diperlukan untuk pembentukan produk lebih
dimasukkan ke dalam mortar dan digerus hingga
lama dan rendemen yang diperoleh relatif rendah
halus kemudian dipindahkan ke dalam gelas kimia
yaitu sekitar 32%. Ini disebabkan kelarutan
100 mL dan ditambahkan 5 tetes air panas. Reaksi
senyawa kompleks yang cukup tinggi dalam air,
kimia segera terjadi yang teramati dengan warna
bahkan dalam air dingin sekalipun. Hasil analisis
larutan menjadi makin gelap. Kemudian sebanyak
unsur-unsur penyusun senyawa kompleks terang-
20 mL etanol ditambahkan ke dalam larutan
kum pada Tabel 1.
tersebut sambil dipanaskan menggunakan pemanas
Karakterisitik adanya ion oksalat dalam
listrik. Pemanasan berlangsung sampai volumenya
senyawa kompleks dapat diamati dari spektrum
menjadi setengah dari volume awal. Setelah itu la-
inframerah. Pada spektrum inframerah senyawa
rutan didinginkan secara perlahan hingga terbentuk
kompleks mononuklir oksalat, adanya ion oksalat
padatan. Padatan yang terbentuk disaring dengan
dapat diamati pada bilangan gelombang 1660 cm–1,
menggunakan kaca masir dan dicuci dengan meng-
dan ikatan ligan oksalat pada ion logam
gunakan etanol dingin. Padatan dikeringkan di
ditunjukkan oleh puncak pada bilangan gelombang
dalam desikator.
520–490 cm–1 and 460–400 cm–1. Selain itu puncak
Sintesis [N(n-C4H9)4][CrFe(C2O4)3].H2O.
lebar pada 3400-3350 cm-1 mengindikasikan
Sebanyak 4,87 gram senyawa kompleks
adanya molekul air. Dalam senyawa kompleks
K3[Cr(C2O4)3]. 3H2O dimasukkan ke dalam gelas
binuklir oksalat, ion oksalat menunjukkan getaran
kimia 100 mL dan dilarutkan dalam 5 mL air.
asimetri ν(C=O) pada 1655 cm-1 dan δ(CO) pada
Larutan dipanaskan menggunakan pemanas listrik,
897 cm-1. Vibrasi pada 1650–1610 cm–1 dan 810–
dan ke dalam larutan ini ditambahkan 2,78 gram
780 cm–1 mengindikasikan ion oksalat sebagai
FeSO4.7H2O sambil diaduk hingga semua padatan
ligan jembatan yang menghubungkan ion-ion
melarut. Pada larutan ini ditambahkan 3,23 gram
logam, dan puncak pada 3300-3500 cm-1
N(n-C4H9)4Br yang telah dilarutkan dengan sedikit
menunjukkan adanya molekul amina kuarterner.
air. Larutan didinginkan perlahan hingga terbentuk
Spektrum inframerah ion oksalat bebas, ion oksalat
padatan yang kemudian dipisahkan dan dicuci
sebagai ligan bidentat dan ion oksalat sebagai ligan
dengan air dingin dan dikeringkan dalam desikator.
jembatan dapat dilihat pada Gambar 2.

8 Jurnal Kimia Indonesia Vol. 1(1), 2006

Sintesis Senyawa Kompleks K[Cr(C2O4)2(H2O)2].2H2O dan [N(n-C4H9)4][CrFe(C2O4)3].H2O

Tabel 1. Hasil Analisis Unsur-unsur Penyusun Senyawa Kompleks

Senyawa Kompleks Komponen Penyusun (%)
K+ Cr3+ C2O42- H2 O
Padatan Merah Ungu 10,95 15,25 52,25 20,75
(11,50) (15,34) (51,52) (21,24)
Padatan Ungu 10,88 15,30 53,05 20,55
(11,50) (15,34) (51,52) (21,24)

Senyawa Kompleks Komponen Penyusun (%)

Cr3+ M2+ C2O42- C H N
[N(n-bu)4][CrCu(ox)3] 8,36 10,15 43,43 42,45 5,77 2,25
(8,36) (10,22) (43,47) (42,47) (5,79) (2,25)
Keterangan : Angka dalam kurung menunjukkan perhitungan teoritis

(a) (b) (c).

Gambar 2 Spektrum inframerah (a). asam oksalat. (b) K[Cr(C2O4)2(H 2O)2].2H2O
(c) [N(n- C4H9)4][CrFe(C2O4)3].H2O

Spektrum elektronik ion Cr3+ pada senyawa segera berubah warnanya menjadi hijau. Demikian
kompleks oktahedral menunjukkan dua serapan pula dengan padatan merah ungu, larut dalam air
maksimum pada daerah tampak yaitu pada panjang menghasilkan warna merah, namun warna larutan
gelombang 418 nm yang sesuai dengan transisi ini segera berubah menjadi berwarna merah ungu
4
T2g ← 4A2g dan pada 588 nm yang sesuai dengan dan akhirnya dihasilkan larutan berwarna hijau
transisi 4T1g ← 4A2g. Puncak yang diamati pada gelap. Warna hijau yang dihasilkan adalah warna
spektrum elektronik kompleks [N(n-bu)4] larutan senyawa kompleks K[Cr(C2O4)3].
[CrFe(C2O4)3].H2O hanya pada 595 nm yang Ketidakstabilan kedua senyawa kompleks ini
menunjukkan transisi 4T1g ← 4A2g ion Cr3+ dalam dalam air sesuai dengan hasil yang telah
medan oktahedral. Puncak kedua untuk transisi dilaporkan oleh Stevenson.5
4
T2g ← 4A2g tidak teramati karena puncak ini Ketidakstabilan senyawa kompleks
terhalangi oleh serapan ion Fe2+ yang sangat tinggi K[Cr(C2O4)2(H2O)2].2H2O bukan hanya dapat
pada panjang gelombang di bawah 400 nm. diamati dalam larutan air saja, namun dapat
Spektrum elektronik senyawa kompleks binuklir diamati juga menggunakan parameter waktu. Pada
tersebut dapat dilihat pada Gambar 3. saat awal sintesis, dihasilkan padatan merah ungu
Senyawa kompleks mononuklir K[Cr(C2O4)2 mengkilap, yang telah diketahui merupakan
(H2O)2].2H2O merupakan senyawa ion 1:1 senyawa kompleks trans-K[Cr(C2O4)2(H2O)2].
sedangkan binuklir [N(n-C4H9)4][CrFe(C2O4)3]. 2H2O. Lima bulan kemudian, warna padatan merah
H2O tidak memiliki daya hantar yang sesuai untuk ungu mengkilap telah berubah warnanya menjadi
senyawa ion, oleh karena itu senyawa binuklir ini ungu. Hal ini menunjukkan bahwa senyawa
disebut kompleks polimer. Data hantaran molar kompleks trans-K[Cr(C2O4)2(H2O)2].2H2O relatif
senyawa kompleks dapat dilihat pada Tabel 2. tidak stabil dibandingkan dengan isomernya, cis-
Padatan ungu larut dalam air menghasilkan K[Cr(C2O4)2(H2O)2].2H2O. Seperti halnya senyawa
larutan berwarna ungu, namun warna larutan ini kompleks mononuklir oksalat yang tidak stabil