Heats of Hydration

d0
502

M+n + 6 H2O

!Hhyd

d5
theoretical line

Aside from electronic absorption data, and magnetic data, is there any other experimental evidence to support covalent bonding within transitionmetal complexes?

645

d10

d3
!Hhyd (kcal/mol)
experimental curve
d
1

d8
d
7

d3

d10

First row Transition Metals (highspin only)

Heats of Hydration

Kinetics of Ligand Exchange

H2O*
H2O* *OH 2

d0
502

M+n + 6 H2O

!Hhyd

+3 H2O*
*OH 2

H2O*
H2O*

+2 H2O*

increasing exothermicity
645

d5
theoretical line

H2O* H2O*
predicted based on coulombic attractive forces only.

Cr

H2O* H2O*

Mn

d10

H2O* exchanged with bulk solvent very slowly (ie, monthes)

H2O* exchanged with bulk solvent very rapidly (ie, seconds)

d3
!Hhyd
(kcal/mol)
*OH 2

H2O* H2O* H2O* Fe

H2O*

+3 H2O*

experimental curve
d1 d3 d5 d7

d8
d10 increasing Zeff (nuclear charge)

First row Transition Metals (highspin only)

H2O* exchanged with bulk solvent fairly rapidly (ie, minutes)

dorbital eg* occupation inuences: Whether or not a structure is distorted (Jahn-Teller)

How do we explain these data?

Stability (rel. stabilities compared using LFSE or CFSE) Bond lengthes/bond strengthes Metal ion size
skip to Jahn-Teller

Ligand Field Stabilization Energy (LFSE)

a measurable quantity (electronic absorp. +6Dq spectroscopy)

z2 x2-y2
useful only for comparing relative stabilities !O= 10 Dq

d3 ion
4Dq

z2 x2-y2 10 Dq +6Dq

dx2-y2 dz2 dxz dyz dxy

random, spherical arrangement of ligands

xz yz xy
ligands xed 90 apart in an octahedral arrangement

4Dq xz yz xy

10Dq= !O

LFSE= (# e 's in t2g ) ( 4Dq) + (# e's in e g*) (+ 6Dq) + + {(# paired e's in ML6 ) (# paired e's in bare M+n )} P

LFSE= 3(4Dq)= 12Dq

d4 ion (high-spin)

z2 x2-y2 10 Dq +6Dq

d5 ion (high-spin)

z2 x2-y2 10 Dq +6Dq

4Dq xz yz xy xz yz xy

4Dq

LFSE= 3(4Dq) 6Dq = 6Dq

LFSE= 3(4Dq) 2(6Dq) = 0

Ligand Field Stabilization Energy (LFSE)

a measurable quantity

z2 x2-y2 10 Dq dx2-y2 dz2 dxz dyz dxy xz yz xy +6Dq

LFSE represents the stability attained upon xing an, otherwise random, arrangment of ligands either 90 (Octahedron) or 109.6 (Tetrahedron) apart

4Dq
skip to LFSE P

LFSE reects the covalent bonding forces that are more directional than coulombic forces There are some forces, ie e/e pairing energy, that disfavor the more directional, xed arrangment of ligands, in some cases.

10Dq= !O

stabilizing

destabilizing

LFSE= (# e 's in t2g ) ( 4Dq) + (# e's in e g*) (+ 6Dq) + + {(# paired e's in ML6 ) (# paired e's in bare M+n )} P
When is the pairing energy important?

d6 ion (high-spin)

z2 x2-y2 10 Dq +6Dq

d6 ion (high-spin)
dx2-y2 dz2 dxz dyz dxy

z2 x2-y2 10 Dq +6Dq

4Dq xz yz xy

4Dq xz yz xy

Free ion LFSE= 4(4Dq) 2(6Dq) = 4Dq

Oh complex
skip to LFSE P

d6 ion (low-spin)
dx2-y2 dz2 dxz dyz dxy

z2 x2-y2 10 Dq +6Dq

d6 ion (low-spin)

z2 x2-y2 10 Dq +6Dq

4Dq xz yz xy

4Dq xz yz xy

Free ion

Oh complex

LFSE= 6(4Dq) +2P = 24Dq + 2P

Lowspin vs. Highspin Octahedral d6 ions

z2 x2-y2 10 Dq dx2-y2 dz2 dxz dyz dxy +6Dq

Lowspin vs. Highspin Octahedral d6 ions

z2 x2-y2 10 Dq dx2-y2 dz2 dxz dyz dxy +6Dq

4Dq xz yz xy

4Dq xz yz xy

Free ion

Free ion

Octahedral complex LFSE(low spin)= 6(4Dq) + 2P = 24Dq +2P

skip to LFSE P

Octahedral complex LFSE(high spin)= 4(4Dq) + 2(+6Dq) = 4Dq

a destabilizing force

The dn congurations which benet the most from ligand eld stabilization energy
dn LFSE (high spin Oh) 4 Dq 8 Dq 12 Dq 6 Dq 0 Dq 4Dq 8Dq 12Dq 6Dq 0Dq LFSE LFSE (low spin Oh) (Td) __________ __________ __________ 16 Dq + P 20 Dq + 2 P 24 Dq + 2 P 18 Dq + P ____________ ____________ ____________ 6Dq 12Dq 8Dq 4Dq 0Dq 6Dq 12Dq 8Dq 4Dq 0Dq
502

Heats of Hydration

d0

M+n + 6 H2O

!Hhyd

d5

Fall on theoretical line when LFSE is zero

d d2 d3 d4 d5 d6 d7 d8 d9 d10

theoretical line
645

d10
LFSE

d3
!Hhyd
(kcal/mol)

experimental curve
d
1

d8
d
7

d3

d10

First row Transition Metals (highspin only)

LFSE is ~10-50 kcal/mol (~ 10%of !Hhyd)

Kinetics of Ligand Exchange

H2O*
H2O* *OH 2

+3 H2O*
*OH 2

H2O*
H2O*

+2 H2O*

Emperical Evidence for LFSE

H2O*

Cr H2O*

H2O*

Mn H2O*

d3 ion

d5 ion
*OH2

H2O*
H2O*

+3 H2O*
*OH2

H2O*
H2O*

+2 H2O*
*OH2

H2O*
H2O*

+3 H2O*

H2O* exchanged with bulk solvent very slowly (ie, monthes)

H2O* exchanged with bulk solvent very rapidly (ie, seconds)

H2O*

Cr H2O*

H2O* H2O*

Mn

Fe H2O*

H2O*

H2O*
*OH 2

+3 H2O*

Fe H2O*

H2O*

H2O*

d5 ion

H2O* exchanged with bulk solvent very slowly (ie, monthes) kex= 2 x 10-6 sec-1 LFSE= 12Dq = 20,400 cm-1

H2O* exchanged with bulk solvent very rapidly (ie, seconds) kex= 2 x 107 sec-1 LFSE= 0

H2O* exchanged with bulk solvent fast (ie, minutes) kex= 2 x 102 sec-1 LFSE= 0
skip to LFSE parameter Dq

H2O* exchanged with bulk solvent fairly rapidly (ie, minutes)

Comparison of tetrahedral vs. an octahedral d2 ions

dn LFSE (high spin Oh) 4 Dq 8 Dq 12 Dq 6 Dq 0 Dq 4Dq 8Dq 12Dq 6Dq 0Dq LFSE LFSE (low spin Oh) (Td) __________ __________ __________ 16 Dq + P 20 Dq + 2 P 24 Dq + 2 P 18 Dq + P ____________ ____________ ____________ 6Dq 12Dq 8Dq 4Dq 0Dq 6Dq 12Dq 8Dq 4Dq 0Dq

Does this mean that d2 ions are more stable in a tetrahedral vs. an octahedral environment?

d2 tetrahedral
LFSE= 12 (Dq)Td (Dq)Td= 4/9 (Dq)Oh LFSE= 12 4/9 (Dq)Oh LFSE= 5 1/3 (Dq)Oh

d2 octahedral
LFSE= 8 (Dq)Oh

d1 d2 d3 d4 d5 d6 d7 d8 d9 d10

The tetrahedral vs. octahedral dorbital splitting diagram

dx2-y2 dz2

Ligand Field Stabilization Energy in Tetrahedral Complexes

xz yz xy dx2-y2 dz2 dxz dyz dxy

t
+4Dq

!t

dxz dx2-y2

dyz dz2

dxy

!o
dxz dyz dxy

10 Dq 6Dq z2

e x -y
2 2

!t ~ 4/9 !o
M

since there is less orbital overlap due to the indirect approach of the ligands

keep in mind, the tetrahedral Dq parameter is much smaller than the octahedral Dq parameter

LFSE(Td)= (#e-s in e)(6Dq) + (#e-s in t)(+4Dq)

Ligand Field Stabilization Energy in Tetrahedral Complexes

xz yz xy dx2-y2 dz2 dxz dyz dxy

t
+4Dq

dn

LFSE (high spin Oh) 4 Dq 8 Dq 12 Dq 6 Dq 0 Dq 4Dq 8Dq 12Dq 6Dq 0Dq

LFSE LFSE (low spin Oh) (Td) __________ __________ __________ 16 Dq + P 20 Dq + 2 P 24 Dq + 2 P 18 Dq + P ____________ ____________ ____________ 6Dq 12Dq 8Dq 4Dq 0Dq 6Dq 12Dq 8Dq 4Dq 0Dq

10 Dq 6Dq z2

e x -y
2 2

keep in mind, the tetrahedral Dq parameter is much smaller than the octahedral Dq parameter

d1 d2 d3 d4 d5 d6 d7 d8 d9 d10

LFSE(Td)= (2)(6Dq) = 12Dq

third electron added to destabilized orbital

dn
z2 x2-y2 10 Dq dx2-y2 dz2 dxz dyz dxy +6Dq
third electron added to stabilized orbital

LFSE (high spin Oh) 4 Dq 8 Dq 12 Dq 6 Dq 0 Dq 4Dq 8Dq 12Dq 6Dq 0Dq

LFSE LFSE (low spin Oh) (Td) __________ __________ __________ 16 Dq + P 20 Dq + 2 P 24 Dq + 2 P 18 Dq + P ____________ ____________ ____________ 6Dq 12Dq 8Dq 4Dq 0Dq 6Dq 12Dq 8Dq 4Dq 0Dq

d2 ion

4Dq xz yz xy

Free ion

Oh complex LFSE(Oh)= 2(4Dq) + 0(+6Dq) = 8Dq

d1 d2 d3 d4 d5 d6 d7 d8 d9 d10

Ligand Field Stabilization Energy in Tetrahedral Complexes

3rd electron
xz yz xy dx2-y2 dz2 dxz dyz dxy

Lowspin vs. Highspin Octahedral d6 ions

z2 x2-y2 10 Dq +6Dq

t
+4Dq

10 Dq 6Dq z2

e x -y
2 2

dx2-y2 dz2 dxz dyz dxy

recall, no such thing as low-spin tetrahedral. Thus the number of paired electrons is never larger than the free ion

4Dq xz yz xy

Free ion

Octahedral complex LFSE(high spin)= 4(4Dq) + 2(+6Dq) = 4Dq

LFSE(Td)= (3)(6Dq) + 3(+4Dq) = 6Dq

Lowspin vs. Highspin Octahedral d6 ions

dn

z2 x2-y2 10 Dq dx2-y2 dz2 dxz dyz dxy +6Dq

d1 d2 d3 d4 d5 d6 d7 d8 d9 d10

LFSE (high spin Oh) 4 Dq 8 Dq 12 Dq 6 Dq 0 Dq 4Dq 8Dq 12Dq 6Dq 0Dq

LFSE LFSE (low spin Oh) (Td) __________ __________ __________ 16 Dq + P 20 Dq + 2 P 24 Dq + 2 P 18 Dq + P ____________ ____________ ____________ 6Dq 12Dq 8Dq 4Dq 0Dq 6Dq 12Dq 8Dq 4Dq 0Dq

4Dq xz yz xy

Free ion

Octahedral complex LFSE(low spin)= 6(4Dq) + 2P = 24Dq +2P

a destabilizing force

Given the LFSEs shown below one would be tempted to say that d3 octahedral complexes would always be more stable than d2 octahedral complexes
dn LFSE (high spin Oh) 4 Dq 8 Dq 12 Dq 6 Dq 0 Dq 4Dq 8Dq 12Dq 6Dq 0Dq LFSE LFSE (low spin Oh) (Td) __________ __________ __________ 16 Dq + P 20 Dq + 2 P 24 Dq + 2 P 18 Dq + P ____________ ____________ ____________ 6Dq 12Dq 8Dq 4Dq 0Dq 6Dq 12Dq 8Dq 4Dq 0Dq

Does this mean that all d3 complexes are more stable than d2 complexes?

d1 d2 d3 d4 d5 d6 d7 d8 d9 d10

[V(H2O)6]+3
LFSE= 8 Dq Dq= 1,800 cm-1 LFSE= 14,400 cm-1

[V(H2O)6]+2
LFSE= 12 Dq Dq= 1,180 cm-1 LFSE= 14,200 cm-1

greater coulombic attraction to +3 ion greater overlap between +3 ion's orbitals and H2O's orbitals

Need to keep in mind: LFSE is expressed in terms of a variable Dq

Conclude
Given that we are comparing compounds with the same M+n oxidation state & row: 1. CFSE always favors the formation of Oh complexes rather than Td 2. The covalent bonding forces in d0, d5 (high spin) and d10 Oh complexes are the smallest 3. As long as P is modest in size, low spin complexes tend to be more stable than high spin complexes 4. d3, d8 and d6 (low spin) favor an Oh complex the most

Importance of Pairing Energy on Complex Stability

py py Fe py py py py
1

+2
OH2 OH2

+2 H2O H2O Fe H2O H2O

SR

4-

P= 10 Dq=

16, 000 cm 20, 000 cm1

18, 000 cm1 16, 000 cm1

SR RS Fe SR RS SR 10, 000 cm1

15, 000 cm1

!o

!o

!o

Lowspin vs. Highspin Octahedral d6 ions

z2 x2-y2 10 Dq dx2-y2 dz2 dxz dyz dxy +6Dq

Lowspin vs. Highspin Octahedral d6 ions

z2 x2-y2 10 Dq dx2-y2 dz2 dxz dyz dxy +6Dq

4Dq xz yz xy

4Dq xz yz xy

Free ion

Free ion

Octahedral complex LFSE(low spin)= 6(4Dq) + 2P = 24Dq +2P

a destabilizing force

Octahedral complex LFSE(high spin)= 4(4Dq) + 2(+6Dq) = 4Dq

Importance of Pairing Energy on Complex Stability

py py Fe py py py py +2
OH2 OH2 +2 H2O H2O Fe H2O H2O

SR

4-

P= 10 Dq=

16, 000 cm1 20, 000 cm1

18, 000 cm1 16, 000 cm1

SR RS Fe SR RS SR 10, 000 cm1

15, 000 cm1

d6 ion (low-spin)
dx2-y2 dz2 dxz dyz dxy

z2 x2-y2 10 Dq +6Dq

4Dq xz yz xy

!o

low spin

!o

!o

Free ion LFSE= 24Dq + 2P= 24(2,000) + 2(16,000)= -16,000 cm-1

Oh complex

Importance of Pairing Energy on Complex Stability

py
z2 x2-y2 10 Dq +6Dq

+2 py py
1

d6 ion (high-spin)
dx2-y2 dz2 dxz dyz dxy

py Fe py py

OH2 OH2

+2 H2O H2O Fe H2O H2O

SR

4-

P= 10 Dq=
4Dq

16, 000 cm 20, 000 cm1

18, 000 cm1 16, 000 cm1

SR RS Fe SR RS SR 10, 000 cm1

15, 000 cm1

xz yz xy

!o

high spin

!o

!o

Free ion

Oh complex LFSE= 4Dq= 4(2,000)= -8000 cm-1 conclude: this cmpd would prefer to be low-spin

Importance of Pairing Energy on Complex Stability

py py Fe py py py py
1

Importance of Pairing Energy on Complex Stability

4py py Fe py py py py
1

+2
OH2 OH2

+2 H2O H2O Fe H2O H2O

1

SR

+2
OH2 OH2

P= 10 Dq=

16, 000 cm 20, 000 cm1

18, 000 cm 16, 000 cm1

SR RS Fe SR RS SR 10, 000 cm1

15, 000 cm
1

+2 H2O H2O Fe H2O H2O

SR

4-

P= 10 Dq=

16, 000 cm 20, 000 cm1

18, 000 cm1 16, 000 cm1

SR RS Fe SR RS SR 10, 000 cm1

15, 000 cm1

!o

!o

low spin

!o

!o

!o

high spin

!o

LFSE= 24Dq + 2P= 24(1,600) + 2(18,000)= 38,400 + 36,000 = -2,400 cm-1

LFSE= 4Dq= 4(1,600)= -6,400

cm-1

conclude: this cmpd would prefer to be high-spin

Importance of Pairing Energy on Complex Stability

py py Fe py py py py
1

Importance of Pairing Energy on Complex Stability

4py py Fe py py py py
1

+2
OH2 OH2

+2 H2O H2O Fe H2O H2O

1

SR

+2
OH2 OH2

P= 10 Dq=

16, 000 cm 20, 000 cm1

18, 000 cm 16, 000 cm1

SR RS Fe SR RS SR 10, 000 cm1

15, 000 cm
1

+2 H2O H2O Fe H2O H2O

SR

4-

P= 10 Dq=

16, 000 cm 20, 000 cm1

18, 000 cm1 16, 000 cm1

SR RS Fe SR RS SR 10, 000 cm1

15, 000 cm1

!o

!o

!o

low spin

!o

!o

!o

high spin

LFSE= 24Dq + 2P= 24(1,500) + 2(10,000)= 36,000 + 20,000 = -16,000 cm-1

LFSE= 4Dq= 4(1,500)= -6,000 cm-1

conclude: this cmpd would prefer to be low-spin

Kinetics of Ligand Exchange

H2O H2O* OH2 +n OH H2O 2 M H2O for Water from the OH2 Exchange Rates

*OH2 +n OH H2O 2 M H2O OH2

LFSE Mn2+ kex= 2 x 107 Zn2+ kex= 2 x 107

kex, sec1 > 104

d5 ion d10 ion

zero zero 12Dq 24Dq + 2P

OH2 OH2 H2O* Metal Primary Coordination Sphere ofH2O Ions, 25 C

Ion Li+ + Na + K Be2+ Mg2+ Ca2+ 2+ Ba kex, sec1 4 x 108 7 x 108 1 x 109 8 x 102 6 x 105 3 x 108 2 x 109 Ion V2+ Cr 2+ Mn2+ Fe2+ Co2+ Ni2+ 2+ Cu Zn2+ kex, sec1 8 x 101 1 x 109 2 x 107 4 x 106 3 x 106 4 x 104 1 x 109 2 x 107 Ion Sn2+ 2+ Hg 3+ Al Fe 3+ Ga3+ Gd3+ 3+ Bi Cr3+ Co3+ Rh3+

4 x 108 1 2 x 102 4 x 102 2 x 109 > 104 2 x 106 < 106 6 x 109

Cr3+ kex= 2 x 10 6 Co3+ kex< 10 6

d3 ion d6 ion (low spin)

The transition-metal complexes stabilized by a large LFSE tend to undergo ligand substitution SLOWLY= substitution inert The transition-metal complexes lacking LFSE tend to undergo ligand substitution RAPIDLY= substitution labile

LFSE Cr2+ kex= 2 x 107 Cu2+ kex= 2 x 107

OH2 H2O H2O +n OH2 M OH2 OH2

hs d4 ion d9 ion

6Dq 6Dq d4 ion (high-spin)

z2 x2-y2 10 Dq +6Dq

weakened bond

4Dq xz yz xy

LFSE= 3(4Dq) 6Dq = 6Dq

LFSE Cr2+ kex= 2 x 107 Cu2+ kex= 2 x 107

OH2 H2O H2O +n OH2 M OH2 OH2

hs d4 ion d9 ion

6Dq 6Dq

Odd # eg* electrons

d9 ion

z2 x2-y2 10 Dq +6Dq

weakened bond
4Dq xz yz xy

Jahn Teller Distorted Structures

LFSE Cr2+ kex= 2 x 107 Cu2+ kex= 2 x 107
OH2 H2O H2O +n OH2 M OH2 OH2

hs d4 ion d9 ion

6Dq 6Dq

Odd # eg* electrons Odd # eg* electrons

+ 1/2 !1 1/2 !1 + 1/3 !2 2/3 !2

distortion is favored for high spin d4
+n H 2O
OH 2

electron is stabilized by 1/2"1

+ 1/2 !1 1/2 !1 + 2/3 !2 1/3 !2

"o

weakened bond

H 2O
OH 2

+n H 2O
OH 2

H 2O

H 2O

H 2O M
H 2O

+n H 2O

Jahn Teller distorted transition-metal complexes tend to undergo ligand substitution RAPIDLY= substitution labile

M H 2O

H 2O

H 2O

H 2O

H 2O

H 2O

compressed

"o > > !1 > !2

elongated

H 2O

Jahn Teller Distorted Structures

+ 1/2 !1 1/2 !1 + 1/3 !2 2/3 !2
distortion is favored for d9
+n H 2O
OH 2

!Which Metal complexes are Labile ?

those containing first row, as opposed to second or third row, metal ions those containing metal ions in their lower oxidation states (ie, M+1, or M+2 vs. M+3 or M+4 ) those for which LFSE= zero (ie, d0, d5 (hs), d10 )

electron is stabilized by 1/2"1

+ 1/2 !1 1/2 !1 + 2/3 !2 1/3 !2

"o

H 2O
OH 2

+n H 2O
OH 2

H 2O

H 2O

H 2O M
H 2O

+n H 2O
skip to LFSE

highspin metals which are subject to Jahn Teller distortions (ie, d4 (hs), d9) In general, the more !* electrons a complex has, the more labile it will be (ie, high spin complexes)

M H 2O

H 2O

H 2O

H 2O

H 2O

H 2O

compressed

"o > > !1 > !2

elongated

H 2O

!Which Metal complexes are Inert ?

those containing second or third row metal ions those containing metal ions in their higher oxidation states (ie, M+3 or M+4 , M+5 ) those for which LFSE=large (ie, d3 , d6 (ls)), and do not possess !* electrons most lowspin complexes