 Awards & Recognition

 What is ligand?
 Chelate
 Chelating ligands
 Applications of Chelation
 Macrocyclic ligand & Macrocyclic effects
 Applications of macrocyclic effects
 Resources
 Jean-Marie Lehn (born 30
September 1939) is a French
chemist. He received the Nobel
Prize in Chemistry together with
Donald Cram and Charles
Pedersen in 1987 for his
synthesis of cryptands. Lehn was
an early innovator in the field of
Supramolecular chemistry.
 And they all are founders of the
field of host–guest chemistry.
 Ligands are ions or neutral
molecules that bond to a central
metal atom.
 Acts as Lewis bases (electron pair
donors), and the central atom acts
as a Lewis acid (electron pair
acceptor).
 Ligands have at least one donor
atom with an electron pair used to
form covalent bonds with the
central atom. HCo(CO)4
 A chemical compound
composed of a metal ion and a
chelating agent. A chelating
agent is a substance whose
molecules can form several
bonds to a single metal ion.
 In other words, a chelating agent
is a multidentate ligand.
 An example of a simple
chelating agent is
ethylenediamine.
 Ligands with two or more points of attachment to metal atoms are called
chelating ligands. And chelating ligands have high affinity for metal ions
relative to ligands with only one binding group.
 Non-chelating ligands such as ammonia (NH3) are monodentate, with one
point of attachment (one tooth). Other ligands are described as bidentate
because they have two points of attachment.
 [Co(H2O)6]2 + 6NH3 ⇌ [Co(NH3)6]2 + 6H2O
[Co(H2O)6]2 + +3en ⇌ [Co(en)3]2 + 6H2O

 The second one involves "condensation" of fewer particles to make the

complex i.e. entropy change for the two reactions are different.
 The Ist reaction has a ΔS° value close to zero, because there are same
number of molecules on both sides of the equation.
 The second one has a positive ΔS° because 4 molecules come together but
7 molecules are produced. The difference between them (ΔS°) is about
+100 J/mol-K.
 DG DH DS D(DG) D(DH) D(DS)

Ni(NH3)22+ -6.93 -7.8 -3

Ni(NH3)42+ -11.08 -15.6 -15

Ni(NH3)62+ -12.39 -24 -39

Ni(en)2+ -10.3 -9.8 +4 -3.1 -1.2 +7

Ni(en)22+ -18.47 -18.3 +3 -7.4 -2.7 +18

Ni(en)32+ -24.16 -28.0 -10 -11.8 -4 +29

~1.3/ring Largest
(small) Effect
 i. Chelate complex formation

OH2 k1 OH2 k2 L
M + L L M M
OH2 k -1 L L k -2 L

A B AB C
 dC k1k 2 [A][B] k -1k -2 [C]
 
dt k -1  k 2 k -1  k 2

ii. The Steady-State Approximation yields:

k 1k 2 k k
dC
 k f [A][B] - k d [C] kf  and k d  -1 -2
dt k -1  k 2 k -1  k 2

Or rewriting with formation (kf) and dissociation (kd) constants:

k 1k 2
kf   k1 (the same as for monodentate ligands)
k -1  k 2
iii. Assuming a chelate effect, k2 >>k-1

k -1k -2 k k
kd   -1 -2
k -1  k 2 k2
iv. kf is not the source of the chelate effect. It is the same as other ligands
 H+ H+ H+ H+
Ni(trien)(H2O)22+ Ni(Htrien)(H2O)23+ Ni(H2O)62+ +
H4trien4+
-1 -1 -1 -1
15 s 4s 2s 2s

v. kd must be the source of the chelate effect (dissociation is slow!).

k-1 is the same as for monodentate ligands and k-2 (ring opening) is the
same as for monodentate ligands: NH3+

Data for k2 (ring closing) N

M
N N N N N N
NH2 ka
Pt +
Pt 2+ ka = 0.73 s-1
N Cl N N

NH3
Pt(NH3)3Cl+ Pt(NH3)4+2 kb = 5.4 x 10-4 M-1s-1
kb

ka 0.73 s 1
 4 1 1
 1.4 x 10 3
M  Effective Concentration
k b 5.4 x 10 M s
Huge Concentration!
k2, the formation of the second M—L bond, has been shown to be extremely large
compared to a second monodentate ligand binding. This is due to the large
“effective concentration” of the second donor atom of a chelate.
NH3
NH2

M NH2 M NH3

chelate monodentate

If k2 is large, kd must be small;

Very fast bond reformation after the first donor dissociates is the kinetic source
of the chelate effect.

vi. Data

M+ L kf kd
Fe2+ HCO2- 7 x 103 10
Fe2+ C2O42- 2 x 104 3 x 10-3
 Provide nutritional supplements.
 Chelation therapy is used to remove toxic metals from the body as
contrast agents in MRI scanning.
 In manufacturing using homogeneous catalysts.
 In chemical water treatment to assist in the removal of metals.
 Acetylacetonate(acac) is an anionic
bidentate ligand that coordinates metal
ions through two oxygen atoms. Acac-
is a hard base so it prefers hard acid
cations.
 With divalent metal ions, acac-forms
neutral, volatile complexes such as
Cu(acac)2 and Mo(acac)2 that are
useful for chemical vapor
deposition (CVD) of metal thin films.
 Crown ethers such as 18-crown-
6 are cyclic hard bases that can
complex alkali metal cations.
Crowns can selectively bind Li+,
Na+, or K+ depending on the
number of ethylene oxide units in
the ring.
 A macrocyclic ligand is a macrocycle with a ring size of at least nine
(including all hetero atoms) and three or more donor sites.
 These exhibit particularly high affinity for metal ions.
 Classic examples are crown ethers and porphyrins.
•12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, diaza-18-crown-6.
 Porphyrins are a group of
heterocyclic macrocycle organic
compounds, composed of four
modified pyrrole subunits
interconnected at their α carbon
atoms via methine bridges
(=CH−).
 The macrocyclic effect is same as the
chelate effect, but the effect is further
enhanced by the cyclic conformation of
the ligand. Macrocyclic ligands are not
only multi-dentate, but they allow less
conformational freedom because they are
covalently constrained to their cyclic
form,. The ligand is said to be "pre-
organized" for binding, and there is little
entropy penalty for wrapping it around the
metal ion.
 Example: heme b is a tetradentate cyclic
ligand which forms a strong complexes
Heme b
with transition metal ions,(in biological
systems) Fe+2.
 Macrocyclic chelate complexes are up 107 times more stable than non-
cyclic chelates with the same number of donors
Ni(trien)2+ + H+ Ni2+ + H4trien4+ t½ = 2 seconds
Ni(cyclam)2+ + H+ Ni2+ + H4cyclam4+ t½ = 2 years

Connecting all of the donors (having no end group) makes k-2 important
 Breaking the first M—L bond requires major ligand deformation
 The increase in Ea required greatly slows down k-2
N
NH2

N
N N N
N N
M M M M
N N N N N N
N N

chelate macrocycle

 A macrocycle is still a chelate, so it still has the k2 chelate effect.

 The result is a very stable complex as kd becomes miniscule.
 Stability follows the order as follows:

Macrocyclic >Chelate >Monodentate

 Ion transport
 Catalysis
 Magnetic Resonance Imaging
 https://chem.libretexts.org
 Supramolecular Chemistry, 2nd edition by J.W. Steed & J.L.
Atwood
 https://en.wikipedia.org