ANO3A Stability HSAB 2018 PDF

Thermodynamics of complex formation,
chelate effect, HSAB
MST - ANO 1
Synthesis of complexes ***
• ‘Bare’ metal ions do not exist!

• E.g. nickel chloride is sold as NiCl2•4H2O
– This is a coordination compound!
– [NiCl2(H2O)4]
• A solution of nickel chloride in water
– Often written as Ni2+(aq)
– This is a complex!
– [Ni(H2O)6]2+
• Complex synthesis always involves
EXCHANGE of ligands
MST - ANO 2
Complex formation ***
Equilibrium reactions
[Ni(OH2)6]2+ + NH3 [Ni(NH3)(OH2)5]2+ + H2O
Equilibrium equation, equilibrium constant

[Ni(NH3)(OH2)5]
K1 =
[Ni(OH2)6][NH3]
Each successive step is an equilibrium

NB: use of [..]; concentration vs complex
MST - ANO 3
Formation or stability constants **
[Cu(OH2)4]2+ + NH3 [Cu(NH3)(OH2)3]2+ + H2O K1
[Cu(NH3)(OH2)3]2+ + NH3 [Cu(NH3)2(OH2)2]2+ + H2O K2
[Cu(NH3)2(OH2)2]2+ + NH3 [Cu(NH3)3(OH2)]2+ + H2O K3
[Cu(NH3)3(OH2)]2+ + NH3 [Cu(NH3)4]2+ + H2O K4
K1 = 104.3; log K1 = 4.3

Individual stability K2 = 103.3; log K2 = 3.3
constants K3 = 102.9; log K3 = 2.9
K4 = 102.3; log K4 = 2.3
Generally: K1 > K2 > K3 > K4
MST - ANO 4
Equilibrium of complexes *
Stability constants known:

 Percentage distribution can be calculated
For [Cu(NH3)n]2+
α1 = [Cu(NH3)1]
[Cu]total
α2 = [Cu(NH3)2]
[Cu]total
etc.
MST - ANO 5
Unusual changes in Kn+1 vs Kn **
Often due to change in coordination number

K1 = 36.3; log K1 = 1.56
K2 = 3.47; log K2 = 0.54
[Cd(H2O)6]2+ + Br− K3 = 1.15; log K3 = 0.06
K4 = 2.34; log K4 = 0.37
Br 2
Br Br
H2O Br
H2O
Cd
Br + Br− Cd
Br
Br
OH2
NB: note different order of magnitude

with previous example
MST - ANO 6
Hg2+ + Cl− *
Intermediate HgCl2 is very stable
K1 = 106.7; log K1 = 6.7

K2 = 106.5; log K2 = 6.5
K3 = 100.9; log K3 = 0.9
K4 = 101.0; log K4 = 1.0
MST - ANO 7
Global/overall stability constant ***
General: M+nL MLn βn
[MLn] βn = K1 K2 ...K(n-1) Kn
βn =
[M][L]n
[Cu(OH2)4]2+ + 4 NH3 [Cu(NH3)4]2+ + 4 H2O β4
[Cu(NH3)4]
β4 = β4 = K1 K2 K3 K4
4
[Cu(OH2)4][NH3]
β4 = 1012.8
log β4 = 12.8
MST - ANO 8
Factors that affect stability ***
• Multidentate vs monodentate ligands

– Chelate effect
– Macrocyclic effect
– Cryptate effect
• HSAB principle
– Hard and Soft Acids and Bases
• Steric factors
MST - ANO 9
Chelate and macrocyclic effect *
H H H
H3N NH3 H2N NH2 N NH2 N N
Cu2+ Cu2+ Cu2+ Cu2+
H3N NH3 H2N NH2 N NH2 N N
H H H
log β4 = 12.8 log K1 = 20.1

log β2 = 19.6 log K1 = 23.3
MST - ANO 10
Metals in biology *
• Metallothionein binds 7 ZnII ions
JACS, 2007, 129, 10911
Hemoglobin (sheep) pH 9.1 (4 subunits)

β4 O2 6.7 x 105 CO binds approx 300x
β4 CO 2.6 x 108 stronger than O2
MST - ANO 11
How many ligands bind to a metal? **
Titration of [Mn(H2O)n(RCOO)2] with bipyridine
1.4
Absorption at 450 nm
2
1.3
1.8 1.2
1.1
1.6 1
0.9
A
1.4 0.8
0.7
1.2
0.6
1 0.5
0.4
0.8 0 1 2 3 4 5
eq bpy
0.6
0.4
0.2
0
350 450 550 650 750
MST - ANO 12
How many ligands bind to a metal?
Titration of [Co(H2O)n(RCOO)2] with bipyridine

Absorption at 450 nm
0.34
1.4
0.32
1.2 0.3
Absorption
1 0.28
0.26
0.8
A
0.24
0.6 0.22
0.2
0.4 0 1 2 3 4
eq. bipyridine
0.2
0
300 400 500 600 700 800
nm
MST - ANO 13
HSAB-principle (Pearson) ***
Hard and Soft Acids and Bases

• Empirically found (basis: covalency)
• Additional effect on electrostatic binding
• Sequences of hardness/softness
• Co-ligands influence hardness/softness
• Can explain and predict events
• Useful with ambidentate ligands; competitions
• Relation with position in Periodic Table
• Relation met ionic radius and with charge
• Relation with polarisability
MST - ANO 14
Electronegativity *
Hard =
more electronegative L
More electropositive M
MST - ANO 15
Hard and Soft Acids and Bases **
Cr6+, Ti4+, Zr4+ F–

Hard
Fe3+, Al3+, Co3+, Ce3+ H2O, R2O, ROH, OH–
Be2+, Mg2+, Ca2+, Ba2+ ClO4–, NO3–, SO42–
H+, Li+, Na+, K+, Cs+ CO32–, RCO2–, PO43–
Sb3+, Bi3+ Cl–, NH3, RNH2, NCS–
Fe2+, Co2+, Ni2+, Cu2+ Br–, ArNH2, py
Ru2+, Rh2+, Ir3+ N3–, NO2–, SO32–
Pt4+, Pd2+, Pt2+ SCN–, CN–, I–
Cd2+, Hg2+, H–, R–, C2H4, Cp–, C6H6
Cu+, Ag+, Au+, Tl+ R3P, R2S, RS–
Soft Rh+, M0 CO, Se2, Se22–
MST - ANO 16
HSAB: compare MeHg+ and H+
MST - ANO 17
HSAB in halide complexes *
Hard
Intermediate
Soft
Log K1 Fe3+ Hg2+
F– 6.0 1.0
Cl– 1.4 6.7
Br– 0.5 8.9
I– - 12.9
MST - ANO 18
Metal-Ligand Exchange Kinetics *
each step can be slow, fast, or diffusion controlled
MST - ANO 19
Lifetime of complexes
[M(OH2)6]n+ + O'H2 → [M(OH2)5(O'H2)]n+ + OH2
F21.1 from Weller

MST - ANO 20
Ligand exchange rates *
MST - ANO 21
Kinetics: lability vs. stability ***
G G TS
TS ΔG‡
ΔG‡
M+P ΔG0 M+P ΔG0
MP MP
labile → low activation barrier inert → high activation barrier
fast ligand exchange rate slow ligand exchange rate
thermodynamic driving force ΔG0 did not change !!!

MST - ANO 22
G TS G TS
ΔG‡ ΔG‡
M+L ΔG0 M+L

ΔG0
ML
ML
unstable → low driving force stable → high driving force
M-L not very strong M-L binding very strong
kinetics did not change !!!
MST - ANO 23
transport proteins G
G (eg, KcsA gate) TS
TS ΔG‡
ΔG‡
M+P ΔG0 M+P
MP ΔG0
MP
Requires: Requires:
High exchange rate Low exchange rate
Low stability structural protein High stability
MST - ANO (eg, zinc finger) 24
Relative Stability of Ligands for Pt ions
stable labile: exchange rapidly

inert stable: strong trans effect
labile labile
intermediate unstable
MST - ANO 25
Summary keywords
• Equilibrium – equation – constant

• Stability constant
– Individual Kn
– Global/overall βn
• Chelate/Macrocyclic effect
• HSAB principle
– Polarizability
MST - ANO 26
Assignment
• Study H9 § 9.3 - 9.6

– p 279-285
MST - ANO 27

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Thermodynamics of complex formation,

chelate effect, HSAB

• ‘Bare’ metal ions do not exist!

Equilibrium equation, equilibrium constant

Each successive step is an equilibrium

[Cu(OH2)4]2+ + NH3 [Cu(NH3)(OH2)3]2+ + H2O K1

[Cu(NH3)(OH2)3]2+ + NH3 [Cu(NH3)2(OH2)2]2+ + H2O K2

[Cu(NH3)2(OH2)2]2+ + NH3 [Cu(NH3)3(OH2)]2+ + H2O K3

[Cu(NH3)3(OH2)]2+ + NH3 [Cu(NH3)4]2+ + H2O K4

K1 = 104.3; log K1 = 4.3

Stability constants known:

Often due to change in coordination number

NB: note different order of magnitude

Intermediate HgCl2 is very stable

K1 = 106.7; log K1 = 6.7

General: M+nL MLn βn

[Cu(OH2)4]2+ + 4 NH3 [Cu(NH3)4]2+ + 4 H2O β4

• Multidentate vs monodentate ligands

log β4 = 12.8 log K1 = 20.1

• Metallothionein binds 7 ZnII ions

JACS, 2007, 129, 10911

Hemoglobin (sheep) pH 9.1 (4 subunits)

Titration of [Mn(H2O)n(RCOO)2] with bipyridine

Titration of [Co(H2O)n(RCOO)2] with bipyridine

Hard and Soft Acids and Bases

Cr6+, Ti4+, Zr4+ F–

each step can be slow, fast, or diffusion controlled

F21.1 from Weller

thermodynamic driving force ΔG0 did not change !!!

M+L ΔG0 M+L

stable labile: exchange rapidly

• Equilibrium – equation – constant

• Study H9 § 9.3 - 9.6

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