DR.

MUHAMMAD
PRESENTED TO
YASIR
AKRAM
Basic Inorganic Chemistry-
II
 BS-CHEMISTRY-6A
Group Leader
Name MUHAMMAD ZEESHAN
Registration Number CHEM18111102

My Group Members

Name Registration number

TAYYAB MEHRAN CHEM18111005
GHULAM RASOOL CHEM18111061
MUHAMMAD WAQAS CHEM18111068
TALHA LIAQAT CHEM18111035
NAVEED ISLAM CHEM18111027
AKKASH JAVAID CHEM18111042
 ANATION REACTIONS
SUBSTITUTION REACTIONS IN OCTAHEDRAL COMPLEXES
 ANATION REACTIONS

In coordination chemistry :
Anation is the "replacement of the ligand water by an anion in a coordination
entity.“
The term is however used more loosely to include displacement of any neutral
ligand by an anion.
The reverse reaction, displacement of an anionic ligand by water, is called
aquation.
[Co(NH3)5(H2O)]3+ + Br− → [Co(NH3)5Br]2+ + H2O
 ANATION REACTIONS

•  

 This type of reaction is important as its behavior indicates not only

how new complexes are formed but also where coordinated water is
replaced by X- :
 ANATION REACTIONS

Generally two observations can be drawn:

1.For a given aqua ion, the rate of anation show little
dependence on the nature of L.

2.The rate constant for anation of a given aqua complex is

almost the same as for H2O exchange.
 MECHANISM FOR ANATION REACTIONS

•  Highly charged cationic complexes tend to form ion-pairs with anionic
ligands
 These ion-pairs undergo reactions via the pathway.
 The electrostatically held nucleophilic incoming ligand can exchange
positions with a ligand in the first coordination sphere, resulting in net
substitution
[Cr(O + SC ⟷ [Cr(O],NC
[Cr(O],NC ⟷ [Cr(ONCS+ O
 MECHANISM FOR ANATION REACTIONS

 Two-step pathway

 Formation of an intermediate

Coordination number of the intermediate is higher than that in the

starting complex
 Mechanism for Anation reactions – Associative
pathway

 Step 1. Collision of ML5X with Y to yield a 7-coordinate intermediate. (slow)

MLnX + Y MLnXY
Step 2. Cleavage of the M-X bond. (fast)
MLnXY MLnY + X
Mechanism for Anation reactions – Associative
pathway
Mechanism for Anation reactions – Associative
pathway
Mechanism for Anation reactions – Associative
pathway
 Mechanism for Anation reactions – Associative
pathway
•  Rate determining step is the collision between original complex and the

incoming ligand Y to form a 7-coordinate intermediate

 The second faster step is the dissociation of X ligand to produce the desired
product.
 The associative mechanism predicts that rate of reaction depends upon the
concentrations of and Y.
 Rate =
 Effect of entering group on Anation Reactions

 Anation reactions do not depend very much on the nature of the entering
group, Y-
 Instead, it is very much dependent on the nature of the bond being
broken.
 Experimental data show that the rate is of the order 10-6 for the different
entering groups (Y-), N3-, SO42-, Cl- or NCS- clearly indicating that the rate
is independent of the nature of the entering group
 Effect of leaving group on Anation Reactions

•  The rate of substitution resction depends on the stability of M-

X bond.
 If the M-X bond is more stable, rate of reaction is low.
 The order of reactivity is
HC > N > > > > S> > SC> N
 This is the order of decreasing thermodynamic stability of the
complexes formed with these groups
 STERIC EFFECTS ON ANATION REACTIONS

 When the non-leaving ligands are bulky, they will be crowding the
central metal ion.
 The incoming ligand will find it difficult to approach the central
metal ion slowing down the rate of reaction taking place by
associative mechanism.
 Why look at water exchange ?

 The study of simple water exchange reactions is valuable given the rate at which
M(H2O)6X+ aqua ions combine with other ligands (L) to form other complexes.
 Shows little or no dependence on L
 Rates for each metal ion are practically the same as the rate of exchange for H2O
on the same metal ion.
 We can use exchange reactions to provide insight into other substitution
reactions.
 REFERENCES

• LIGAND SUBSTITUTION REACTIONS. (2021, MARCH 10). RETRIEVED MARCH 20,

2021, FROM HTTPS://CHEM.LIBRETEXTS.ORG/@GO/PAGE/188714\
• WIKIPEDIA CONTRIBUTORS. (2019, MARCH 26). ANATION. IN WIKIPEDIA, THE FREE
ENCYCLOPEDIA. RETRIEVED 16:10, MARCH 20, 2021, FROM HTTPS://
EN.WIKIPEDIA.ORG/W/INDEX.PHP?TITLE=ANATION&OLDID=889542569
•  IUPAC, COMPENDIUM OF CHEMICAL TERMINOLOGY, 2ND ED. (THE "GOLD BOOK")
(1997). ONLINE CORRECTED VERSION:  (2006–) "ANATION
• GHOSH, M. C.; BHATTACHARYA, P.; BANERJEE, P., "ANATION REACTIONS OF
COBALT(III) COMPLEXES", COORDINATION CHEMISTRY REVIEWS 1988, 91, 1-34.
• HTTPS://PEOPLE.CHEM.UMASS.EDU/CJOSEPH/CHEM241/LECTURE15.PDF
• HTTP://WWWCHEM.UWIMONA.EDU.JM/COURSES/MBC21JNOTES.PDF
THANK YOU
M.Zeesha
n