Isomers and Nomenclature

Geometric isomers molecules with same atom

connectivities but different arrangements in space
dichlorobenzene
3 isomers: ortho, meta, para
tetraamminedichlorocobalt(III) ion
only 2 isomers
 Octahedral geometric isomers - 2

Two isomers of triamminetrichlorochromium(III)

meridional facial

mer-[Cr(NH3)3Cl3] fac-[Cr(NH3)3Cl3]
 Four coordinate geometric isomers
Tetrahedral geometry more common
dichloromethane (tetrahedral) one isomer

Some metal complexes square-planar

diamminedichloroplatinum(II): two isomers
 Overview of Coordination numbers
2: uncommon, d10 ions, linear
Ag(NH3)2+, CuCl2, Hg(CH3)2

3: rare, planar Pt(PPh3)3 (d10)

4: common
tetrahedral (minimises ligand-ligand repulsion)
FeCl4, Zn(NH3)42+, MnO4

planar, special conditions, mainly d8

Pt(NH3)42+, PtCl42, AuCl4
or macrocyclic ligands: porphyrins, etc
 Coordination numbers - 2
5: uncommon
trigonal bipyramid: Fe(CO)5, Co(CN)53
square pyramid: BrF5, V=O(H2O)42+
fluxional (Berry pseudo-rotation)

6: most common: octahedron, a few trigonal prisms

7, 8, 9: unusual, early transition metals, fewer d es

ZrF73, Mo(CN)83, ReH92
Slide 28 of 96
 Constitutional or Structural Isomers
(different atom connectivities)
1. Coordination isomers which ligands coord?
CrCl3.6H2O
[Cr(H2O)6]Cl3
[Cr(H2O)5Cl]Cl2.H2O accidental waters
[Cr(H2O)4Cl2]Cl.2H2O of hydration

[Cr(NH3)6][Co(CN)6] or [Co(NH3)6][Cr(CN)6]

2. Linkage isomers which atom is coordinated?

thiocyanate (NCS): N-bonded or S-bonded
[Co(NH3)5NCS]2+
pentaammine-N-thiocyanatocobalt(III) ion
 Linkage Isomers

N- bonded nitro isomer (-NO2-)

pentaamminenitrocobalt(III) ion

O-bonded nitrito isomer (-ONO-)

pentaamminenitritocobalt(III) ion
 Optical Isomerism
Optical isomers (enantiomers) objects without a
centre of symmetry (or other improper rotation
axis) can exist in non-superimposable mirror
image forms. Same physical properties, except
rotation of plane polarised light
Recall from Chem 1:
Enantiomers of Lactic Acid

CH3
CH3

H
H
OH
COOH HOOC OH

(S)-Lactic Acid (R)-Lactic Acid

 Optical Isomerism - 2
1. Tris(bidentate) complexes: eg [M(en)3]

(right) (left)

Right-handed screw turn clockwise into

paper, anti-clockwise to remove (as shown)

http://www.people.carleton.edu/~mcass/TrisChelates/Index.html
 Optical Isomerism - 3
2. [Co(en)2Cl2]+

cis isomer optically active, trans isomer not

 References and Exam Questions
Winter, Chapter 3; Silberberg, Section 23.4;
S&A, Chapter 8

Sketch the possible isomers of the

dichlorobis(1,2-ethanediamine)cobalt(III) and the
bis(1,2-ethanediamine)platinum(II) ions (1,2-
ethanediamine = ethylenediamine).

Explain how the existence of only two isomers

of [Co(NH3)3Br3] allows the inference of an
octahedral geometry around the Co, as opposed
to a planar geometry.