Inorganic chemistry with Walter Chiambah

D-BLOCK ELEMENTS
INTRODUCTION
 D-block elements are located between group II and III on the periodic table.
 These elements share properties with S-block and P-block elements.
 They can form both ionic and covalent compounds.
 Applications include manufacturing tools, electric cables, and jewelry.
 Important roles in biological systems as catalysts (enzymes) and in oxygen transport (hemoglobin,
myoglobin).
 Some elements serve as food supplements.

What are d-block elements and transition elements?

Ans: D-block elements are elements whose valence electrons are entering the inner d-subshell.

 The first d-block series includes elements from scandium to zinc.

Element Symbol Atomic Number Electronic Configuration

Scandium Sc 21 [Ar] 3d¹ 4s²
Titanium Ti 22 [Ar] 3d² 4s²
Vanadium V 23 [Ar] 3d³ 4s²
Chromium Cr 24 [Ar] 3d⁵ 4s¹
Manganese Mn 25 [Ar] 3d⁵ 4s²
Iron Fe 26 [Ar] 3d⁶ 4s²
Cobalt Co 27 [Ar] 3d⁷ 4s²
Nickel Ni 28 [Ar] 3d⁸ 4s²
Copper Cu 29 [Ar] 3d¹⁰ 4s¹
Zinc Zn 30 [Ar] 3d¹⁰ 4s²

Why are electrons removed from the 4s before the 3d?

 The 4s orbital is lower in energy than the 3d orbital (according to the Aufbau principle).
 However, the 3d orbital is closer to the nucleus, and when an electron enters the 3d orbital, it repels 4s
electrons to a higher energy level.
 Hence, electrons are removed from the 4s orbital before the 3d.

Why is the electronic configuration of chromium [Ar] 3d⁵ 4s¹ and not [Ar] 3d⁴ 4s²?

 Half-filled 3d⁵ and 4s¹ orbitals are more stable due to Hund's rule compared to partially filled 3d⁴ and
fully filled 4s².

Explain why the electronic configuration of copper is 3d¹⁰ 4s¹ and not 3d⁹ 4s².

 Completely filled 3d¹⁰ and half-filled 4s¹ are more stable than partially filled 3d⁹ and fully filled 4s².

Electrons in Boxes for D-block Elements

 Inorganic chemistry with Walter Chiambah

Electronic Configuration for Some Ions in the D-series

Exercise: Calculate the oxidation state of each d-element in the compound below and use box
notation to write the electronic configuration.

Scandium and zinc are d-block elements but are not transition elements. Explain.

Note: Transition elements form at least one stable ion with a partially filled d-subshell.

 Scandium forms only one stable ion with an empty d-orbital.

 Zinc forms only one stable ion with a completely filled d-subshell.
 This explains why scandium and zinc do not form variable oxidation states.
 Their compounds are white, unlike transition metal compounds, which are coloured.
 Scandium and zinc show little catalytic activity and are usually diamagnetic, while transition metal
compounds are often paramagnetic or diamagnetic.
 Inorganic chemistry with Walter Chiambah

Physical Properties of Transition Elements

i) Atomic Radius

 Decreases from scandium to copper due to an increase in effective nuclear charge.

The decrease is only slight because electrons are added to the inner d-orbital, shielding the outer s-electrons
from the increasing nuclear charge.

 The flattening of the curve from vanadium to copper is due to minimum volume occupied by atoms.
 The increase in atomic radius from Cu to Zn is due to shielding of outer S-electrons by completely filled
d-electrons.

ii) Ionisation Energy

 The first ionisation energy increases from scandium to zinc due to an increase in effective nuclear
charge and a decrease in atomic radius.
 The increase is only slightly because electrons are added to the inner d-orbital, which shields the outer s-
electrons from the increasing nuclear charge.
 Minor peaks and troughs are due to stability achieved from half-filled or completely filled orbitals.
 Inorganic chemistry with Walter Chiambah

iii) Melting and Boiling Point

Transition elements typically have higher melting and boiling points than s-block elements due to stronger
metallic bonds and a decrease in atomic radius.

 Melting point increases from scandium to chromium due to increased strength of metallic bonds from
unpaired electrons.
 Melting points decrease from iron to zinc due to fewer paired electrons in metallic bonding.
 Manganese has a lower melting point than chromium due to the half-filled 3d electrons and completely
filled 4s electrons being less available for bonding.

Characteristics of Transition Elements (Metals)

 They have Variable oxidation states
 They form complex ions
 They form coloured compounds
 They have Catalytic activities
 They are Paramagnetic and diamagnetic properties

Variable Oxidation State

 Inorganic chemistry with Walter Chiambah
 Transition elements, except scandium and zinc, have variable oxidation states because the 3d and 4s
electrons are similar in energy and can participate in bonding.

Oxides and Chlorides of Transition Elements

Element Oxide Formula Chloride Formula Common Oxidation States
Sc Sc₂O₃ ScCl₃ +3
Ti TiO, TiO₂ TiCl₃, TiCl₄ +2, +3, +4
V V₂O₅, V₂O₃ VCl₃ +2, +3, +4, +5
Cr CrO, Cr₂O₃, CrO₃ CrCl₃ +2, +3, +6
Mn MnO, Mn₂O₃, MnO₂, Mn₂O₇ MnCl₂, MnCl₃ +2 to +7
Fe FeO, Fe₂O₃ FeCl₂, FeCl₃ +2, +3
Co CoO CoCl₂ +2, +3
Ni NiO NiCl₂ +2
Cu CuO, Cu₂O CuCl, CuCl₂ +1, +2
Zn ZnO ZnCl₂ +2

Common oxidation state

Observations on Oxidation States

 +3 oxidation state is common at the beginning of the series (Ti, V, Cr, Mn).
 +2 oxidation state is common toward the end of the series (Fe to Zn).
 Maximum oxidation state corresponds to the number of unpaired d-electrons plus s-electrons.
 Manganese can exhibit +7 oxidation state because it has 7 valence electrons in 3d and 4s orbitals.
 From iron to zinc, maximum oxidation state is not attained due to stronger nuclear attraction on the 3d
electrons.

Question: why is the +3 oxidtion state common at the beginning of the transition series while the +2 is
common toward the end?

This is because across the series, there an increase nuclear charge which binds
the d-electrons more tightly hence only the weakly held 4s electrons are involved in bonding

Formation of Complex Ions

 Inorganic chemistry with Walter Chiambah
What is a complex ion?

 A complex ion is a metal ion surrounded by an anion or neutral molecule (ligand) with a lone pair of
electron called ligand

What is a ligand?

A ligand is an anion (negatively charged ion) or neutral molecule with at least one lone pair of electrons that can
be donated to the central metal ion (CMI) to form a coordinate (dative) covalent bond.

 Most ligands are Lewis bases (electron pair donors).

 The central metal ion acts as a Lewis acid (electron pair acceptor).

Why do transition elements form complexes?

Because they are small and highly charged, with availability of low-lying d-orbitals for coordinate bond
formation.

 In complex formation, the lone pairs of electrons on ligands are donated to the vacant d-orbital of
thetransition metal ion.

Coordination Number

The coordination number is the number of dative bonds the central metal ion forms with ligands.

 Example: tetraamminecopper(III) ion has coordination number 4.

Types of Complexes

 Anionic Complex: Overall negative charge (e.g., [Fe(CN)6]4−, [Fe(CN)_6]4-, [Fe(CN)6]4−)

 Cationic Complex: Overall positive charge (e.g., [Co(NH3)6]3+, [Co(NH_3)_6]3+, [Co(NH3)6]3+)
 Inorganic chemistry with Walter Chiambah
 Neutral Complex: Overall charge zero (e.g., [Ni(CO)4], [Ni(CO)_4], [Ni(CO)4])

Types of Ligands

 Monodentate Ligand: Donates one lone pair (e.g., Cl⁻, NH₃)

 Bidentate Ligand: Donates two lone pairs (e.g., ethylenediamine, en)
 Polydentate Ligand: Donates more than two lone pairs (e.g., EDTA, hexadentate)

Chelating Ligand

This is a ligand that forms a ring structure with the central metal ion.

 The complex formed is called a chelate.

 Example: tris(ethylenediamine)cobalt(III) ion [(Co(en)3]3+.

Charge of a Complex

 The charge of a complex is the algebraic sum of the charges of ligands and the central metal ion.
 Neutral ligands contribute zero charge.

Calculating Oxidation State in Complexes

Ligand Charge
Halogens (Cl⁻, Br⁻) -1
Oxalate (C₂O₄²⁻) -2
EDTA -4
H₂O, NH₃, CO, NO, en 0

Examples: Calculate the oxidation state of the transition metal in the complexes below
 Inorganic chemistry with Walter Chiambah
2−
 a. [Cu(CN)4] , b. [Cr(H2O)3Cl3], c. K4[Fe(CN)6], d. [Co(NH3)6]Cl3

Naming Complexes
i) Determine overall charge to classify as cationic, anionic, or neutral complex (in cases where it is not given)
ii) Name cation before anion.
iii) Name ligands:

 Anionic ligands end in -o (e.g., fluoro, chloro, bromo, cyano)

 Neutral ligands use molecule name except H₂O (aqua), NH₃ (ammine), CO (carbonyl), NO (nitrosyl)

iv) Use Greek prefixes for number of identical ligands (di-, tri-, tetra-, etc.)
v) For ligands with Greek prefixes, use bis-, tris-, tetrakis- etc. with brackets.

Metal Naming Rules

 Cationic complexes use English metal name.

 Anionic complexes add suffix -ate (e.g., chromate, ferrate). Use Latin names if available (e.g., ferrum
→ ferrate).
 Inorganic chemistry with Walter Chiambah

Indicate Oxidation State of the Central Metal Ion

 Indicate the oxidation state of the central metal ion In Roman numerals. Do not separate the name of
the metal from the oxidation state. E.g Copper(III), Manganese(VII).
 Write name of the ligands, the name of the central metal ion, the oxidation state of the central metal
ion in that order as one word.

E.g [Co(H2O)4Cl2]= tetraaquadichlorocobalt(III) ion

Alphabetical Order of Ligands

 When there are two or more ligands of different kinds in a complex, write them in alphabetical order
without considering the Greek prefixes when naming. E.g di, tris, tetrakis etc.

Complex Formulas

 Enclosed in square brackets except when only oxygen and chlorine ligands are present. Any element
outside the square bracket is separated from the name of that complex.
 When writing the formula of a complex from it name, anionic ligands are written first before. Neutral
ligands (either case is still accepted)

Exercise
Name the complexes below
1. [Co(H2O)6]2+
2. [Co(C2O4)3]3-
3. [Ni(en)2]2+
4. [Cu(EDTA)]2-
5. [Fe(CN)6]3-