CHEMISTRY DIGITAL ASSIGNMENT

NAME: AAHAN DEY

REG NUMBER: 24BBT0022
COURSE: ENGINEERING CHEMISTRY (BCHY101L)
FACULTY: ASHOK KUMAR S.K
TOPIC: INTRODUCTION TO INORGANIC COMPLEXES – STRUCTURE AND
APPLICATIONS
 INTRODUCTION TO INORGANIC COMPLEXES – STRUCTURE AND
APPLICATIONS

Inorganic complexes are chemical compounds in which a central metal atom/ion is bonded to
ligands, which can be ions/molecules surrounding it by coordinate covalent bonds. The structure
is determined through coordination numbers and geometry, which in turn, lead to the observed
properties and reactivity of the complexes. Theories such as Crystal Field and Ligand Field
Theory were proposed in an attempt to explain their electronic structures and behavior.
As a whole, inorganic complexes are of immense importance in chemistry, having applications
in biological systems and industrial production of materials, making them very useful.

Key Points:

1. Factors deciding the properties:

Nature of the metal, its oxidation state, and the type of ligands.
2. Structure:
 a. The arrangement of ligands around the central metal defines the geometry of the
complex (e.g., linear, tetrahedral, octahedral).
b. The coordination number and ligand size govern these structures.
3. Theoretical Foundations:
Crystal Field Theory (CFT) and Ligand Field Theory explain how metal-ligand
interactions influence electronic structure, stability, and reactivity.
4. Significance in Nature and Industry:
a. Inorganic complexes are fundamental in biological systems (e.g., hemoglobin for
oxygen transport, chlorophyll for photosynthesis).
b. Industrial applications include catalysts for chemical reactions, water purification,
etc.
5. Technological and Medical Applications:
Complexes are vital in medical treatments (e.g., cisplatin for cancer therapy),
imaging techniques (e.g., gadolinium complexes in MRI), and renewable energy
(e.g., dye-sensitized solar cells).

HISTORY OF INORGANIC COMPLEXES

Early Observations and Uses

Potassium alum (KAl(SO4)2) was used in dyeing, tanning and even purifying water as early as
1500BCE.
One of the first well understood coordination complexes, Prussian blue (Fe7(CN)18) was first
synthesized by the paint maker Johann Jacob Diesbach in Berlin around 1706. The pigment is
believed to have been accidentally created when he used potash tainted with blood to create
some red cochineal dye. The original dye required potash, ferric sulfate, and dried cochineal.
Instead, the blood, potash, and iron sulfate reacted to create a compound known as iron
ferrocyanide, which, unlike the desired red pigment, has a very distinct blue hue.

Prussian blue
 Structure of Prussian blue

The properties of complexes were first understood following the work of Christian Wilhelm
Blomstrand in 1869. He developed what is now known as the complex ion chain theory. In
considering metal amine complexes, he theorized that the ammonia molecules compensated for
the charge of the ion by forming chains of the type [(NH3)X]X+, where X is the coordination
number of the metal ion. He compared his theoretical ammonia chains to hydrocarbons of the
form (CH2)X.
However, much of this was disproved by Alfred Werner in 1893.
 Alfred Werner
Alfred claimed that if the ions were to form a chain, this would occur outside of the coordination
sphere while the ions that bound directly to the metal would do so within the coordination
sphere. He discovered the spatial arrangements of the ligands that were involved in the formation
of the complex hexacoordinate cobalt. His theory allows one to understand the difference
between a coordinated ligand and a charge balancing ion in a compound, for example the
chloride ion in the cobaltammine chlorides and to explain many of the previously inexplicable
isomers. He introduced the concept of the primary valence (oxidation state) and secondary
valence (coordination number).
 FACTORS AFFECTING PROPERTIES OF INORGANIC COMPLEXES

The properties of inorganic complexes like color, stability, reactivity, magnetism, and geometry,
are influenced by several factors, including the central metal ion and the ligands surrounding it.

1. Central Metal Ion

The nature of the metal ion affecting the properties of the complex:

a. Oxidation State:

• Higher oxidation states increase the electrostatic attraction between the metal ion and
ligands, resulting in stronger bonding.
• Example: [Fe(CN)6]3- is less stable than [Fe(CN)6]4- due to Fe3+ being smaller and more
positively charged than Fe2+.

b. Electronic Configuration:

• The d-electron count influences geometry, magnetism, and ligand binding.

• Example: d8 metals (e.g., Ni2+, Pt2+) tend to form square planar complexes, while d10
metals like Zn2+ form tetrahedral ones.

c. Ionic Radius:

• Smaller metal ions create stronger metal-ligand bonds due to higher charge density.
• Example: Fe3+ forms more stable complexes compared to Fe2+ .

d. Nature of the Metal (Transition vs. Non-Transition):

• Transition metals can form complexes with a variety of geometries and oxidation states
due to their partially filled d-orbitals.
• Non-transition metals usually have limited flexibility and weaker ligand field effects.

2. Ligand Characteristics

Ligands type and behavior affecting the properties:

a. Nature of the Ligand:

• Strong Field Ligands: Such as CN-, CO tend to form strong metal-ligand bonds and
low-spin complexes.
• Weak Field Ligands: Such as H2O, Cl- tend to form weak metal-ligand bonds and high-
spin complexes.

b. Denticity (Number of Donor Atoms):

• Polydentate ligands (e.g., EDTA, en) increase complex stability due to the chelating
effect.
• Example: [Cu(EDTA)]2-is more stable than [Cu(H2O)6]2+

c. Ligand Size and Steric Effects:

• Bulky ligands can cause steric hindrance, distorting geometries or limiting the number of
ligands bound to the metal.
• Example: Tertiary phosphine ligands like PPh3 lead to lower coordination numbers.

d. Charge on the Ligand:

• Negatively charged ligands (e.g., Cl- ,CN-) form stronger bonds due to greater
electrostatic attraction.

3. Coordination Number and Geometry

The number of ligands attached to the central metal and their arrangement influence the
complex's properties:

• Higher Coordination Numbers: Usually lead to increased stability but may require
larger ligands.
• Geometry: Octahedral, tetrahedral, and square planar shapes affect electronic
distribution and reactivity.

4. Crystal Field Stabilization Energy (CFSE)

The splitting of metal d-orbitals by ligands in a coordination complex (explained by Crystal Field
Theory) affects:
 • Color: Due to electronic transitions between split d-orbitals.
• Stability: Higher CFSE values correspond to more stable complexes.
• Magnetic Properties: High-spin vs. low-spin configurations affect the number of
unpaired electrons.

5. Spectrochemical Series

The ligands’ ability to split d-orbitals follows the spectrochemical series, influencing properties
like:

• Color: Strong field ligands produce larger splitting, shifting absorption to longer
wavelengths.
• Spin: Strong-field ligands lead to low-spin configurations, while weak-field ligands lead
to high-spin configurations.

6. Macrocyclic Effects

• Macrocycles increase stability due to entropy and pre-organization effects.

• Example: Macrocyclic complexes like porphyrins (Fe-porphyrin in hemoglobin) are
extremely stable.

STRUCTURE OF INORGANIC COMPLEXES

Coordination Number and Geometry

The coordination number (CN) of a metal ion indicates the number of ligands directly attached to
it. The typical geometries associated to their respective coordination numbers:
a. Coordination Number 2: Linear

• Many electron-rich d10 ions, viz: Cu+, Ag+, and Au+, form linear complexes.
• Example: [Ag(NH3)2]+

b. Coordination Number 3: Trigonal Planar

• Observed in complexes with steric constraints or due to specific ligand interactions.

• Example: Fe[N(SiMe3)3]3

c. Coordination Number 4:

• Tetrahedral Geometry:
 o Most tetrahedral complexes are high spin, even with strong field ligands.
o Example: [CoBr4]2-, Ni(CO)4, [Cu(py)4]+
• Square Planar Geometry:

o Prevalent in metal ions with d8 configuration. Most are low spin even with weak
field ligands.
o Example: [RhCl(PMe3)3], [IrCl(CO(PMe3)2,] cisplatin(PtCl2(NH3)2)

d. Coordination Number 5:

• Trigonal bipyramidal:
 o Central atom is surrounded by three neighbors that form a trigonal plane around
it. The last two neighbors are above and below this plane.
o Example: PCl5
• Square pyramidal:

o Central atom sits above a base of four neighbors; those four positions form a
square plane together. A fifth atom occupies the space above the central atom.
o Example: VO(OH2)4
e. Coordination Number 6: Octahedral Geometry

• Most common coordination number for transition metals.

• Example: [Co(NH3)6]3+, [Ni(CN)6]4-, and [Fe(H2O)6]2+

f. Higher Coordination Numbers (6+):

• Present in complexes with relatively large metal ions (lanthanides and actinides) and
small ligands.
• Example: IF7, Mo(CN)84−
APPLICATIONS OF INORGANIC COMPLEXES
1. Medicinal Applications

Role in healthcare and medicine:

a. Anti-Cancer Agents

• Platinum-based complexes, such as cisplatin [PtCl2(NH3)2], are widely used for

chemotherapy.
• They bind to DNA, causing cross-linking and disrupting cancer cell replication.
b. Diagnostic Imaging

• Gadolinium(III) complexes (e.g., [Gd(DTPA)]2−) are used as contrast agents in Magnetic

Resonance Imaging (MRI).
c. Anti-Microbial and Anti-Parasitic Agents

• Silver complexes are used for their antimicrobial properties.

• Complexes of arsenic and antimony are effective against parasitic diseases like
leishmaniasis.

d. Enzyme Mimics

• Zinc complexes mimic metalloenzymes like carbonic anhydrase, aiding in CO 2 hydration.

e. Metal-Based Drug Delivery

• Ruthenium complexes are explored for targeted drug delivery systems.

2 Industrial Applications

Inorganic complexes are used various industries by their unique reactivities and properties:
a. Pigments and Dyes

• Chromium and cobalt complexes are used in paints, ceramics, and glass for vibrant
colors.
• Complexes of ruthenium and osmium are used in dye-sensitized solar cells.

b. Electronics

• Organometallic complexes are used in light-emitting diodes (OLEDs) for displays.

c. Metallurgical Processes

• Cyanide complexes like [Au(CN)2]- are employed in gold extraction via leaching.

3. Biological Roles

Inorganic complexes occur naturally in biological systems and are essential for life processes:

a. Oxygen Transport

• Hemoglobin, an iron porphyrin complex, transports oxygen in blood.

• Myoglobin stores oxygen in muscle tissues.
b. Electron Transfer

• Cytochromes, copper, and iron-sulfur clusters facilitate electron transfer in cellular

respiration.

c. Nitrogen Fixation

• Molybdenum-containing complexes in nitrogenase enzymes convert atmospheric

nitrogen to ammonia.

d. Photosynthesis

• Magnesium in chlorophyll is essential for capturing light energy.

REFERENCES

1. Lawrance, Geoffrey A. (2010). Introduction to Coordination Chemistry. Wiley.

2. Hermann, Andreas; Lein, Matthias; Schwerdtfeger, Peter (2007). "The Search for the
Species with the Highest Coordination Number"
3. De, A.K. (2003). A Text Book of Inorganic Chemistry.
4. Structure & Reactivity in Organic, Biological and Inorganic Chemistry (Schaller)
5. Inorganic Chemistry (Saito)
6. Science Direct Magazine