Dr. Paul Mushonga: Course Title: Inorganic Systems and Metal Clusters

Course code: HCH416
Course Title: INORGANIC SYSTEMS AND METAL

CLUSTERS
Part A: Heterocyclic Inorganic Systems
Dr. Paul Mushonga.

Rm 205, Chemistry New Wing
Department of Chemistry
UNIVERSITY OF ZIMBWE
Email: [email protected]
Office Hours: Tue 14:00-15:30;

Thu 14:30-15:30
or by appointment.
Paul
MUSH
Wade-Mingos-Lauhrer Rules
• The 14n rule is extremely useful in classification transition

metal carbonyl clusters
• The idea is to compare the baseline reference value (14n) with

the total valence electrons of the cluster
2
Paul
MUSH
Considering Os3(CO)12, determine the structure type
n = 3
Baseline reference, 14n = 42
Total Valence Electron Count = 3(8) + 12(2)
= 48
Thus baseline reference is less by 6,
Therefore the cluster series = 14n + 6 (ARACHNO)
Considering [Os6(CO)18]2- , determine the structure type

n = 6
Total Valence Electron Count = 6(8) + 18(2) +2
= 86
3 Therefore the cluster series = 14n + 2 (CLOSO)
Paul
MUSH
• Considering Co6(CO)16 , determine the structure type
n = 6
Total Valence Electron Count = 6(9) + 16(2)
= 86
Therefore the cluster series = 14n + 2 (CLOSO -TYPE)
4
Paul
MUSH
2.3 CAGES AND DERIVATIVES OF THE P4 STRUCTURE
5
Paul
MUSH
CHAINS – LAYERED ALUMINOSILICATES
6
Paul
MUSH Zintl PHASES
• A Zintl phase or Zintl cluster, named after a German Chemist
Edward Zintl, is a product of a reaction between an
electropositive group 1 or 2 metal and an electronegative p-
block metal or metalloid from groups 13, 14, 15 or 16
• Zintl phases are not alloys – they are ionic compounds with
electron transfer from the electropositive metal to the more
electronegative element
• Zintl phases lie intermediate in the triangle of bonding

between purely metallic bonding found in alloys (where the
difference in electronegativity between the metal atoms is
small) and ionic solids (which have a larger difference in
electronegativity)
7
Paul
MUSH Zintl PHASES
Bonding triangle applied as a classification

scheme for the different types of crystalline
solids (Taken from Principles of Inorganic
Chemistry)
8
Paul
MUSH
Zintl PHASES
• The main characteristics of Zintl phases are
– They consists of an alkali or alkaline-earth metal and a p-
block element (or elements) which can be a metal, semi-
metal or a small-gap semiconductor
– They are closed-shell compounds which are electronically

balanced such that the number of electrons needed for
covalent bonding in the structure is equal to the total
number of electrons provided by the constituent elements
– They are semi-conductors or poor conductors
– They are either diamagnetic or possess very weak

temperature independent paramagnetism
9
– They are brittle compounds having high melting points
Paul
MUSH
• As with the boranes, the bonding in Zintl phases is delocalized,

and many of the negatively charged Zintl ions exist as
deltahedral clusters
• The anions in these Zintl phases are referred to as the ‘Zintl

ion’ having a complete octet of valence electrons and are
polymeric in nature, the cations are located within the anionic
lattice.
• Examples of Zintl ions are the structures of the nido-[Ge9]4-

10
and [Sn5]2- given above
Paul
MUSH
• Other structures of Zintl ions are shown below:
11
Paul
MUSH
Zintl IONS – Determining structures using Wade’s Rules
• The 4n rule (where n is the number of vertices) can be used to
predict the structures of the Zintl phases
12
Paul
MUSH
Zintl IONS – Determining structures using Wade’s Rules
• The 4n rule (where n is the number of vertices) can be used to
predict the structures of the Zintl phases
Main Group No. of Structural Shape
Cluster Framework Type
Atoms
4n + 2 6 Closo Octahedral
4n + 2 5 Closo Trigonal Bipyramidal
4n + 4 5 Nido Square pyramidal
4n + 6 4 Arachno Butterfly
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Paul
MUSH
Example 1: Use Wade’s rule to predict the shape of the following

Zintl ions:
(i) Pb52-
(ii) Sb42-
Pb52-: Sb42-
Solution: Total Valence Electron Count Solution: Total Valence Electron Count
(VEC) (VEC)
= (No. of atoms)(Valence e- ) = (No. of atoms)(Valence e- ) +
+ (e- from –ve charge) (e- from –ve charge)
= (5)(4) + (2) = (4)(5) + (2)
= 22 = 22
= (4n + 2) [because n = 5] = (4n + 6) [because n = 4]
∴ Closo structure and trigonal ∴ Arachno structure and square
bipyramidal geometry geometry
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Course code: HCH416

Course Title: INORGANIC SYSTEMS AND METAL

Dr. Paul Mushonga.

Office Hours: Tue 14:00-15:30;

• The 14n rule is extremely useful in classification transition

• The idea is to compare the baseline reference value (14n) with

Considering [Os6(CO)18]2- , determine the structure type

• Zintl phases lie intermediate in the triangle of bonding

Bonding triangle applied as a classification

– They are closed-shell compounds which are electronically

– They are semi-conductors or poor conductors

– They are either diamagnetic or possess very weak

• As with the boranes, the bonding in Zintl phases is delocalized,

• The anions in these Zintl phases are referred to as the ‘Zintl

• Examples of Zintl ions are the structures of the nido-[Ge9]4-

• Other structures of Zintl ions are shown below:

Example 1: Use Wade’s rule to predict the shape of the following

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