, SECTION 1 – Introduction
1) Electron structure
Remember that:
1s 1s
2s 2p • 4s fills before 3d
3s 3p • 4s also empties before 3d (in ions)
4s 3d • Cr is [Ar] 4s1 3d5
•
Cu is [Ar] 4s1 3d10
• Give the electron structure of the following atoms / ions.
Fe [Ar] ……………………………………… Cu [Ar] ………………………………………
Fe3+ [Ar] ……………………………………… Cu+ [Ar] ………………………………………
Sc [Ar] ……………………………………… Cu2+ [Ar] ………………………………………
Sc3+ [Ar] ……………………………………… Zn [Ar] ………………………………………
V [Ar] ……………………………………… Zn2+ [Ar] ………………………………………
V2+ [Ar] ……………………………………… Cr [Ar] ………………………………………
2) What is a transition metal?
transition metal = element that has an incomplete d sub-shell in either its atoms or one its common ions
metal atom Common ions Transition metal?
Sc Sc [Ar] ………………. Sc3+ [Ar] ……………….
Cu Cu [Ar] ………………. Cu+ [Ar] ………………. Cu2+ [Ar] ……………….
Zn Zn [Ar] ………………. Zn2+ [Ar] ……………….
NB – This is the latest IUPAC definition, but some exam boards incorrectly state that it is an element that has an incomplete
d sub-shell in one of its common ions (and excludes the atoms part) – this only affects scandium in reality but make
sure you are aware if your exam board does this.
3) Properties of transition metals
The incomplete d sub-shell is responsible for a number of general properties of transition elements:
1) variable oxidation states
2) catalytic action
3) coloured compounds
4) formation of complexes
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, SECTION 2 – Complex ions
1) Some definitions
Ligand = particle with lone pair of electrons that bonds to metals by a co-ordinate bond
Complex = metal ion with co-ordinately bonded ligands
Co-ordination number = number of co-ordinate bonds from ligands to metal ion
Lewis base = lone pair donor
Lewis acid = lone pair acceptor
2) Formation of complexes
Common, simple ligands include H2O, NH3 and Cl– ions, all of which have a long pair
of electrons. Complexes are formed when ligands such as these form co-ordinate
bonds using their lone pairs to a metal ion.
In this example, 4 chloride ions (Cl-) act as ligands, each forming a single co-ordinate
bond to the Cu2+ ion using a lone pair, forming the [CuCl4]2- ion.
Ligands are acting as Lewis bases when they bond to transition metals as they
donate a lone pair to form a co-ordinate bond. The metal ion acts as a Lewis acid as
it accepts lone pairs.
3) Shapes of complexes
The table shows the most common shapes of complexes.
linear square planar tetrahedral octahedral
co-ordination
2 4 4 6
number
shape M M M 109.5 M
180 90 90
With larger ligands
(e.g. Cl–) Most complexes
Pt2+ and Ni2+
occurrence Ag+ complexes with small ligands
complexes
(when ligands are (e.g. H2O, NH3)
too big for six to fit)
[Ag(NH3)2]+
example [PtCl4]2- [CuCl4]2- [Cu(H2O)6]2+
(in Tollen’s reagent)
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, 4) Types of ligands
All ligands must have one (or more) lone pair(s) of electrons to form the co-ordinate bond(s) to the metal ion.
Unidentate ligands – ligands which form one co-ordinate bond to a metal ion
Ligand :Cl– :OH– :CN– H2O: :NH3
Example complex [CuCl4]2- [Cr(OH)6]3- [Ag(CN)2]- [Fe(H2O)6]2+ [Cr(NH3)6]3+
Bidentate ligands – ligands which form two co-ordinate bonds to a metal ion
1,2-diaminoethane (en) ethanedioate ion (C2O42-)
Ligand O O
CH2 CH2 C C
- -
H2N: :NH2 O: :O
O
NH2 O C
Example 3+ C O 3-
complex H2N NH2 O O C O
Cr Cr
H2N NH2 O O C O
NH2 C NH
O 2
O C
O
[Cr(NH2CH2CH2NH2)3]3+
[Cr(C2O4)3]3-
Multidentate ligands – ligands which form more than two co-ordinate bonds to a metal ion
EDTA4- forms 6 bonds porphyrin forms 4 bonds
Ligand
-
:OOC CH2 CH2 COO:-
:N CH2 CH2 N:
-
:OOC CH2 CH2 COO:-
How it globin
bonds
N:
N: Fe2+ :N
:N
O2 or H2O
Example [Cu(EDTA)]2- haemoglobin
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