Review of variable valence

 Transition metal ions have variable oxidation

state
 Electron configurations
 4s23dn with some exceptions
Isomerism – same atoms, different
arrangement
 Constitutional and stereo
 Constitutional
 Different connections between the atoms
 Linkage isomers (choice of linkage atom)
 Ionization isomers (different anion bonding)
 Stereoisomers
 Same connections but different spatial
arrangements
 Diastereoisomers (geometric isomers)
 Enantiomers (handedness)
 Linkage isomers
 The nitrite ion can use either the O or the N atom as the ligand
since both have non-bonding pairs.
 Indicate linkage in the name:
 Nitro (NO2) links through N
 Nitrito (ONO) links through O
 Obvious influence on physical properties
 Ionization isomers
 Different anions are linked to the central atom

 In one, the free anion is SO42-

 In the second, the free anion is Br-

CoNH  Br SO
3 5 4

CoNH  SO Br
3 5 4
 Diastereo (geometric) isomers
 Same attachments but different arrangement
 Cis- and trans- (analogous to bonding in alkenes)
 Influences physical properties through different polarity

 Example with square planar: opposite or side-by-side

Octahedral complex
 Not all complexes qualify for
geometric isomers
 Square planar –
 ML2X2 (cis and trans)
 ML3X (none)
 Tetrahedral – none with any composition
 Octahedral –
 ML4X2 (cis and trans)
 ML3X3
 ML5X (none)
 More than two ligands…

 ML2XY or ML4XY can also have cis and trans

isomers
Isomers or equal?
 What hands are these…?
 Apparently all same connections and yet…
 Enantiomers are molecules or ions that form
mirror images of each other
 Tetrahedral C atoms with four different groups
 Hands are enantiomers.
 They possess chirality
 Molecules that have no handedness are achiral
 Testing for chirality
 Presence of planes of symmetry – achiral
 Absence of plane of symmetry – chiral
Handedness in complexes with
bidentate ligands
 How many diastereoisomers and enantiomers are
there of Co(en)2Cl2+?
 Getting a complex?
 Which are chiral?
 Which are achiral?
 What are the enantiomers?