Transition Metal Coordination Chemistry

Prof S.M.Draper 2.05 SNIAMS Building smdraper@tcd.ie

What is a transition metal?

Recommended books

M.J. Winter, d-block Chemistry, Oxford Chemistry Primers, OUP, 2001 M.S. Silberberg, Chemistry, 3rd Ed, McGrawHill, 2003 (chapter 23)

C.E. Housecroft, A.G. Sharpe, Inorganic Chemistry, 1st Ed, PrenticeHall, 2001 J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry, 4th Ed., HarperCollins, 1993

z Shapes of d-orbitals y x

Electrons in atoms 4s Sc Ti 3d 4p

z z y x z y x x y

V Cr Mn Fe Co

yz

xz

xy

x2-y2

z2

Ni Cu Zn

Working out numbers of d-electrons from oxidation states: 1st: how many electrons are there in the shell? - count along the periodic table e.g. Mn = 7 electrons Cu = 11 electrons

How many d-electrons has the metal?

1 2 3 4 5 6 7 8 9 10 11 12

O ox =
-O

O O-

en = H2N NH2

2nd: how many electrons are lost? - oxidation state e.g. Mn(VII) = 7 electrons lost Cu(II) = 2 electrons lost complex [Cr2O7]2[MnO4]3rd: how many electrons left over? - subtract e.g. Mn(VII) = Cu(II) = [Ag(NH3)2]+ [Ti(H2O)6]3+ [Co(en)3]3+ [PtCl2(NH3)2] [V(CN)6]4Hence the only valance electrons available in a transition metal ion are d-electrons [Fe(ox)3]3-2 +3 d5 -1, 0 +2 d8 0 +3 d1 O.S. of L -2 -2 O.S. of M +6 +7 no. d electrons d0 d0

Colour of transition metal complexes biological activity magnetic behaviour colour Ruby Corundum Al2O3 with geometry impurities

Whats interesting about Transition Metal Complexes??

Sapphire Corundum Al2O3 with and impurities octahedral metal centre coordination number 6

coordination number oxidation states

medical applications

Emerald Beryl AlSiO3 containing Be with impurities

Haemoglobin O2

Oxygen carrier in blood Porphyrin-Fe transition metal complex Fe(II) ion is octahedrally coordinated
NN N N Fe NN Fe N N

Cisplatin [PtCl2(NH3)2]

Coordination number 6

HO 2C HO 2C

NR NR
2 HO 2 C

HO C

square planar Pt(II) coordination number 4 cis-isomer

the first of a series of platinum coordination complex-based anti-cancer drugs (Platinol-AQ)

Alfred Werner - Nobel Prizewinner 1913

[Co(NH3)6]Cl3 3+

[Co(NH3)5Cl]Cl2 2+

[Co(NH3)4Cl2]Cl +

CoCl3 . 6NH3 CoCl3 . 5NH3 CoCl3 . 4NH3 CoCl3 . 3NH3

yellow purple green

xs Ag+ xs Ag+ xs Ag+ xs Ag+

3 moles AgCl 2 moles AgCl 1 mole AgCl 1. 0 moles AgCl 2. 3. The metal is in a particular The complex has a fixed (primary valancy) (secondary valancy) Werner's conclusions

The ligands are bound to the metal via a bond which resembles a covalent bond

Lewis Acid-Base Concept: parallel with main group chemistry

Adducts formed by the reaction of metal ions (Lewis acids) with several ligands (Lewis bases).
H Ni2+ + H 2O H O . .: Ni NH 3 Ni 2+ 2+ 2+

What is a coordination complex?

n+/-

X+/n

NH 3 :NH 3

6 :NH 3

H 3 N: NH 3

Ni

Central metal ion or atom surrounded by a set of ligands

NH 3

The ligand donates two electrons to the d-orbitals around the metal forming a

Properties of products differ from those of separate reactants (i.e., colour, composition, magnetic properties, etc.).

1 3

F H N
zz z z

F
z z z z

NH3

BF3

L L L

L L

= coordinate or dative bond

zz

z z

zz

z z

zz

z z

z z

zz z z z z

zz

zz

B N H

F H

F H

B N H

F H

e.g. [Co(NH3)6]3+

_ H N > BF
3

NH3
zz

3+
z z

3
zz z z

N H

Co3+

H3N H3N
z z

z z

NH3
z z

NH3

zz

NH3

Group 14

CO carbon monoxide e.g. NH3, H2O, OH-, CO32Small donor atoms CO, PPh3, C2H4, SRH, CN-, SCNLarger donor atoms Less electronegative Easily polarisable

H H Group 15 H N NH3 ammonia

P

Electronegative PPh3 phosphine Not very polarisable

H Group 16 O H

R H2O water S R SR2 thioether e.g. Fe(III), Mn(II), Cr(III) Small metals (1st row) High oxidation state e.g. Ag(I), Cu(I) Larger metals (2nd + 3rd row) Low oxidation state

 - bonded ligands

Group 14

z z

CNcyanide

Phphenyl K+ Cl

Cl Pt Cl CH2 CH2

H2C

CH2

Group 15

z z

NOnitrous

z z

NCSisocyanate [PtCl3(2-C2H4)]-

RC

CR

Group 16 O H

OHhydroxide

z z

SCNthiocyanate

Monodentate Group 17 X halide H hydride Bidentate Tridentate Multidentate three many

donor atom per ligand donor atoms per ligand donor atoms per ligand donor atoms per ligand

Neutral bidentate ligands: 2 donor atoms

Anionic bidentate ligands

-donor bidentate ligand

O
H 2N
zz

O O oxalate = ox2Fe C O C C O O

NH2
zz

e.g. [PtCl2(en)]

1,2-diaminoethane = ethylene diamine = en

O H 3C O

acetate = ac-

[Fe(CO)3(4-C4H6)]

Ph2P

zz

PPh 2
zz

N
zz

N
zz

OH N O R'

N
zz

N
zz

O M C N H

O N C H

Pd
R' O HO N R

1,2-diphenylphosphineethane dppe

2,2'-bipyridine bpy

1,10-phenanthroline phen

Pd(II)-oxime complex

Tridentate ligands: three donor atoms

Tetradentate ligands

Hexadentate ligand tetraanion of

H 2N

zz

NH
zz

zz

NH2

N N
zz zz

NH2 N
N
zz

ethylenediaminetetraacetic acid EDTA

NH2

NH2

O O O O

tris(2-aminoethyl)amine diethylenetriamine dien 2,2':6',2"-terpyridine tpy

N

tren

O O O
N N HN

1,2,4-triazacyclonane macrocyclic ligand

HN

zz

zz

NH

NH N

N
N

NH N N

HN

N H
porphyrin

zz

phthalocyanin

Inner coordination sphere = Outer coordination sphere =

H2O H2O H2O

Mn2+

SO42H2O

H2O OSO3
Mn2+

OH2 OH2

H2O H2O

OH2

H2O

[Mn(OH2)6][SO4]: outer sphere complex

[Mn(OH2)5(SO4)5]: inner sphere complex

Ligand Exchange Reactions [Fe(OH2)6]2+ 2+ + + + + CN[Fe(OH2)5(CN)]+ + H2O

hexaaquo iron(II) complex

cyanide ion

K1

const [H2O]

[Fe(OH2)5(CN)+] [H2O] [Fe(OH2)62+] [CN-]

The reaction continues. [Fe(OH2)5(CN)]+ K2 + CN[Fe(OH2)4(CN)2]+ [Fe(OH2)4(CN)2] + H2O

The reaction continues.

[Fe(OH2)4(CN)2] + CN[Fe(OH2)3(CN)3]+ H2O
3 = [Fe(OH2)3(CN)3-] [Fe(OH2)62+] [CN-]3 [Fe(OH2)2(CN)42-] [Fe(OH2)62+] [CN-]4

[Fe(OH2)3(CN)3]- + CN-

[Fe(OH2)2(CN)4]2- +

H2O

4 =

[Fe(OH2)5(CN)+] [CN-]
[Fe(OH2)2(CN)4]2- + CN[Fe(OH2)(CN)5]3+ H2O
5 =

[Fe(OH2)(CN)53-] [Fe(OH2)62+] [CN-]5 [Fe(CN)64-] [Fe(OH2)62+] [CN-]6

K1K2

[Fe(OH2)5(CN)+] = [Fe(OH2)62+] [CN-]

[Fe(OH2)4(CN)2] [Fe(OH2)5(CN)+] [CN-]

[Fe(OH2)(CN)5] + CN[Fe(CN)6]4+ H2O
6 =

Overall Stability Constant

[MLn] [M] [L]n

Stability constants are often expressed in log form ie log n

Values of n

The Chelate Effect

2+

4-

+ 6

+ 6

[M(NH3)6]2+
H3N H3N

NH3 M NH3 NH3 NH3

n+
H2 N N H2

H2N M H2N NH2 NH2

n+

[M(en)3]2+

[Fe(CN)64-] [Fe(OH2)62+] [CN-]6

~ 1035 [M(OH2)6]n+ [M(OH2)6]n+ + + 6 NH3 3 en [M(NH3)6]n+ + [M(en)3]n+ + 6 H2O 6 H2O

log 6 = 35

Kn < < K3 < K2 < K1

Entropy of chelate formation Go = -RT ln K [Cu(OH2)6]2+ + 2 NH3 2107.7 Ho = - 46 kJ mol-1

Go = Ho - TSo [Cu(OH2)4(NH3)2]2+ log 2 = 7.7 So = - 8.4 J K-1mol-1 + 2 H2O

Go = Ho - TSo

Enthalphy changes similar [M(OH2)6]n+ [M(OH2)6]n+ + + 6 NH3 3 en

Entropy changes differ [Cu(OH2)6]2+ + [M(NH3)6]n+ [M(en)3]n+ + + 6 H2O 6 H2O 2 1010.6 log 1 = 10.6 Ho = - 54 kJ mol-1 So = + 23 J K-1mol-1 en [Cu(OH2)4(en)]2+ + 2 H2O

So is large and positive

- TSo is large and negative

Thermodynamic vs Kinetic Stability The Macrocyclic Effect Complexes containing macrocyclic rings have enhanced stability compared to acyclic ligands

2+ H N Cu N H2 N H2 N H

2+ H N Cu H N N H N H

e.g cf. log K1 = 23.9 acyclic chelating ligand log K1 = 28.0 macrocyclic ligand

[Cr(OH2)6]3+ [Fe(OH2)6]3+

d3 hs d5

kinetically inert kinetically labile

slow substitution of Ls rapid substitution of Ls

(thermodynamic stability similar)

G always favours formation of macrocyclic complex

Tour of Coordination Numbers and their Geometries The Kepert Model The shape of a complex is usually dictated by the number of coordinated atoms. The coordinated atoms are as far away from each other as possible. bonding electrons are ignored. Non-

Most Common Geometries of Transition Metal Complexes

Tetrahedral

109o 28'

C.N. 4

Square Planar

90o

C.N. 4

Note: regular geometries are often distorted structural features of multinuclear complexes are described in terms used for individual metal centres when energy differences between different structures are small, fluxional behaviour may be observed

Trigonal bipyramidal

120o + 90o

C.N. 5

Square based pyramidal

90o

C.N. 5

Octahedral

90o

C.N. 6

Coordination number 2 Cu(I), Ag(I), Au(I), Hg(II)

Coordination number 5

[CuCl2]180o

[Au(CN)2]-

trigonal bipyramid

square-based pyramid

90o

90o

Coordination number 3

120o [HgI3]CN Cu

[Cu(CN)2]CN Cu C N Cu CN C N

C N Cu CN C

120o

The two structures have very similar energy

trigonal bipyramid
Cl Cl Cu Cl Cl Cl
3-

square-based pyramid
3-

CN NC NC Co CN CN

[CuCl5]3-

[Co(CN)5]3-

N N Co Br N N

O O O V

O O

[Co(Me6tren)Br]+

[VO(acac)2]

Tetrahedral complexes

Favoured by steric requirements

optical isomerism
1 2 3 1 2 3

[CoCl4

]2non-superimposable mirror images

[MnO4]90o 109o [NiCl4]2-

Square planar geometry

Square Planar Geometry

e.g. [PtCl4]2[AuBr4][Co(CN)4]2cisplatin

Square planar complexes are formed by i.e. group 10 Ni2+, Pd2+, Pt2+ Au3+ cis-[PtCl2(NH3)2] cis-diamminedichloroplatinum(II)

trans-[PtCl2(NH3)2] trans-diamminedichloroplatinum(II)

Square planar complexes are formed by e.g. CN-

Coordination number 6

Octahedral geometry [ML4X2]

Geometrical Isomerism

e.g. [Mn(OH2)6]2+ [Cr(CO)6]

trans-[Co(NH3)4Cl2]+ Staggared ligands vs. Eclipsed ligands green

cis-[Co(NH3)4Cl2]+ violet

C+

C+

do metals e.g. WMe6

Octahedral geometry [ML3X3]

Geometrical Isomerism

Octahedral geometry [M(2L)2X2] e.g. [Co(en)2Cl2]+

Geometrical and Optical Isomerism

trans geometrical isomer

H N N H Cl Co Cl N H H N

mer-[Co(NH3)3(NO2)3] cis geometrical isomer two optical isomers

fac-[Co(NH3)3(NO2)3]

Non-superimposable mirror images = and enantiomers

Octahedral geometry

Optical Isomerism

Tetragonal Distortion:
Tetragonal elongation z-axis

2+ [M(2L)3]
N N N N Ru N N

2 long axial & 4 shorter equatorial bonds [Cu(OH2)6]2+, [Cr(OH2)6]2+

Tetragonal compression z-axis 2 short axial & 4 longer equatorial bonds trans-[Co(NH3)4(CN)2]+

M [Ru(bpy)3]2+

* Small distortion but symmetry lower than octahedral.

Trigonal Distortion:
Two faces on opposite sides of octahedron move either towards or away from each other
Structural Isomerism

Isomerism

Stereoisomerism Isomers have the same M-L bonds, but the atoms are arranged differently in space

Isomers have the same empirical formula but the atoms connectivities

N N Elongation Rotate by 60 N N M N N

differ

Ionisation isomerism Hydration isomerism

Geometrical isomerism cis/trans mer/fac Optical isomerism and

Complexes of tacn can show this type of distortion [M(tacn)2]2+

Coordination isomerism Linkage isomerism

N N N
tacn = 1,3,7-triazacyclononane

Polymerisation isomerism

Ionisation isomerism Exchange of a ligated anion with a counterion

Coordination isomerism

[Cu(NH3)4][PtCl4] no ppt Ag+ AgBr [Co(NH3)5(SO4)]Br [Co(NH3)5Br]SO4 Ba2+ Ba2+ BaSO4 [Co(NH3)6][Cr(CN)6] no ppt Polymerisation isomerism Solvate isomerism Exchange of a neutral ligand for an anionic ligand e.g. [Co(OH2)6]Cl3 violet light green dark green e.g. [Pt(NH3)4][PtCl4]

[Pt(NH3)4][CuCl4] [Cr(NH3)6][Co(CN)6]

square planar

octahedral

[Pt(NH3)2Cl2]

[Co(OH2)5Cl]Cl2

Both polymers have the empirical formula [Pt(NH3)2Cl2]n

[Co(OH2)4Cl2]Cl

Linkage isomerism

Higher Coordination Numbers

Coordination Number 7 h [Co(NH3)5(NO2)]2+ yellow nitro-complex [Co(NH3)5(NO2)]2+ red nitrito-complex

[Pd(NCS)2(PPh3)2] isocyanate

[Pd(SCN)2(PPh3)2] thiocyanate

[WBr3(CO)4)](distorted)

[TaF7]2[ZrF7]3-

Coordination Number 8

Na3[Mo(CN)8]

(nBu4N)3[Mo(CN)8]

Coordination Number 9

[ReH9]2-

Shapes of d-orbitals

z orthogonal y x z z y y x x x

Symmetrical ligand field

z M x and y

z y

x2-y2 yz Energy z2 x2-y2 yz z2 xz xy

z2

xz xy

yz

xz

xy

x2-y2

Effect of ligand field on metal d-orbitals

The difference in energy between the eg and the t2g energy levels is the . This is given the value 10 Dq.

symmetrical field

octahedral ligand field

eg
o or 10 Dq

t2g

Electron configurations: d1 ion e.g. [Ti(OH2)6]3+ violet solution in water

3+

The nature of oct [Ti(OH2)6]3+

490-580 nm

one d-electron in a t2g orbital the complex has a Crystal Field Stabilisation Energy (CFSE) of - 0.4 oct Absorption spectrum: max = 510 nm = 243 kJ mol-1

d4 ions e.g. [V(OH2)6]3+ + 0.6 oct - 0.4 oct CFSE = = - 0.6 oct

e.g. [Cr(OH2)6]3+

+ 0.6 oct CFSE = - 0.4 oct = - 1.6 oct + P

High and Low spin Complexes High spin complex Low spin complex

Factors affecting the magnitude of oct

e.g.

[Fe(OH2)6]2+ [Co(OH2)6]2+

oct = 10 000 cm-1 oct = 9 700 cm-1

[Fe(OH2)6]3+ [Co(OH2)6]3+

oct = 14 000 cm-1 oct = 18 000 cm-1

is small electrons occupy eg and t2g orbitals singly before pairing

is large electrons pair in t2g oribtals before occupying eg orbitals e.g. [Co(NH3)6]3+ [Rh(NH3)6]3+ [Ir(NH3)6]3+ oct = 22 900 cm-1 oct = 34 100 cm-1 oct = 41 000 cm-1

eg eg I- < Br- < S2- < SCN- Cl-< NO3- < F- < OH- < ox2t2g < H2O < NCS- < CH3CN < NH3 en < bpy < phen NO2- < PR3 < CN- CO

t2g

M.J. Winter, d-block Chemistry, p.83

Octahedral Crystal Field

ions, Oh field

d-orbital energies in + 0.6 oct - 0.4 oct

free ion

spherical ligand field

octahedral ligand field

x2-y2 yz

z2 xz

xy + 0.6 oct

x2-y2 yz

z2 xz

xy

- 0.4 oct

the complex has a Crystal Field Stabilisation Energy (CFSE)

ions, Oh field

ions, Oh field High Spin eg + 0.6 oct t2g - 0.4 oct t2g eg

+ 0.6 oct - 0.4 oct

Low Spin eg + 0.6 oct t2g - 0.4 oct + 0.6 oct - 0.4 oct

ions, Oh field eg + 0.6 oct t2g - 0.4 oct

ions, Oh field eg + 0.6 oct t2g - 0.4 oct

eg 1. What is the CFSE of [Fe(CN)6]3-?

eg. 2. If the CFSE of [Co(H2O)6]2+ is -0.8 oct, what spin state is it in?

ions, Oh field + 0.6 oct t2g - 0.4 oct Only configurations

can be high or low spin

Jahn-Teller Distortion

z y x

Jahn-Teller Distortion z-out: d-orbitals with z-component are stabilised Oh field

eg

+ 1/2 1 - 1/2 1 oct + 2/3 2

t2g The complex ligands contract or elongate giving a - 1/3 2

Jahn-Teller Distortion z-in: d-orbitals with z-component are destabilised Oh field

Jahn-Teller Theorum "For a nonlinear molecule in an electronically degenerate state distortion must occur to lower the symmetry, remove the degeneracy and lower the energy"

x2-y2 + 1/2 1 eg x2-y2 z2 - 1/2 1 oct + 1/3 2 t2g yz xz xy - 2/3 2 e.g. [Cu(OH2)6]2+ Cu(II) = d9 z-out t2g eg x2-y2 z2 z2 xy yz xz xy yz xz Cr2F5 Oh z-out Cr(II) = high spin d4 e.g. K2[CuF4] Oh z-in z-out

Na2[CuF4] Oh

Square planar geometry: ML4 Oh z-out square planar x2-y2

eg

x2-y2 x2-y2 z2 z2 xy z2

t2g

xy yz xz xy yz xz

yz xz d8 complexes: some Ni(II), and Pd(II), Pt(II)

Tetrahedral crystal field splitting

Splitting of d-orbitals in a tetrahedral crystal field eg

oct metal ion in free space in symmetrical field

t2g

x2-y2 yz z2 xz xy

Effect of crystal fields on complex geometry

Spin orbit coupling is particularly significant for metals lower in the periodic table but for 1st row transition metal complexes the formula can be used in a simplified form because: The spin contribution outweighs the orbital angular momentum contribution to eff" Spin only magnetic moment, SO

SO =

n (n + 2)

where n = number of unpaired electrons

SO = 2

S (S + 1)

where S = total spin quantum number = n / 2

Spin only magnetic moment, SO Measurement of magnetic susceptibility SO = n (n + 2) where n = number of unpaired electrons Gouy Balance What is the spin only magnetic moment of ..?
eg x2-y2 z2

[Co(OH2)6]2+ n= SO = =
yz xz t2g xy

pivotal balance scale

yz

xz e

t2 xy

[NiCl4]2x2-y2 z2

sample

n=

SO =

=
x2-y2

magnetic field

[Ni(CN)4]2n= SO = =
yz

xy z2 xz

Values of eff for high spin Oh complexes Effective magnetic moment, eff From experimentally measured molar magnetic susceptibility, m M ion dn S SO(BM) 0 1.73 2.83 3.87 4.90 5.92 4.90 3.87 2.83 1.73 0 obs (BM) 0 1.7 - 1.8 2.8 - 3.1 3.7 - 3.9 4.8 - 4.9 5.7 - 6.0 5.0 - 5.6 4.3 - 5.2 2.9 - 3.9 1.9 - 2.1 0

Sc3+, Ti4+ Ti3+ V3+ V2+, Cr3+ Mn3+

d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10

0
1/ 2

1
3/ 2

Cr2+,

2
5/ 2

Mn2+, Fe3+ Fe2+, Co3+ eff in Bohr Magnetons: B = eh = 4 me 9.27 x 10-24 J T-1 2.83 is the magnetogyric ratio T is temperature in Kelvins Co2+ Ni2+ Cu2+ Zn2+

2
3/ 2

1
1/ 2

Colour in TM complexes [Ti(OH2)6]3+

Colour of d-d transitions depends on magnitude of

Absorption spectrum: max = 510 nm

white light 400-800 nm

490-580 nm

The Colour Wheel If red light is absorbed

Blue: 400-490 nm yellow-green: 490-580 nm Red: 580-800 nm

the complex appears green If purple light is absorbed the complex appears yellow wavelength, (nm)

Effect of magnitude of on colour 1. For a given ligand, the colour

Effect of magnitude of on colour

2. For a given metal ion, the colour depends on [V(H2O)6]3+ [V(H2O)6]2+

violet light absorbed complex appears yellow

yellow light absorbed complex appears violet

3+

2+

Colour and the Spectrochemical Series

Weak Field Ligands High Spin Complexes

Strong Field Ligands Low Spin Complexes

I- < Br- < S2- < SCN- < Cl-< NO3- < F- < OH- < ox2small < H2O < NCS- < CH3CN < NH3 < en < bpy < phen < NO2- < phosph < CN- < CO large

Transition Metal Coordination Chemistry

Professor Sylvia Draper smdraper@tcd.ie
WHERE HAVE WE BEEN ? WHERE ARE WE GOING ?

[Ti(H2O)6]3+
490-580 nm

Absorption spectrum: max = 510 nm

eg

h
t2g

eg
o

t2g

Lecture 7: Magnetism and Colour Tetrahedral crystal field Magnetism Spin only magnetic moment Magnetism measurements Absorption of light d1 complexes and colour Effect of on colour

Lecture 8: Colour continued, and Ligand Field Theory Selection rules Limitations of CFT LFSE and Thermodynamic aspects of LFT

Factors affecting magnitude of 1. 2. 3. Oxidation state of metal e.g. Position of metal in periodic table Type of ligand in spectrochemical series

Intensity of colour depends on ..

The Intensity of the colour depends on Selection Rules and is measured by the absorbance
Absorbance is defined by the Beer-Lambert equation: A = log10(I0/I) = .c.l where A = absorbance I0 = intensity of incident light; I = intensity of light after passing through the cell; = molar absorption coefficient; c = concentration; l = cell pathlength. Typical Spectrum: Octahedral Cr(III) complex [Cr] = 0.002M
Absorbance

0.25

1. 2.

Laporte Selection Rule Spin Selection Rule

Calculation of :

?
At 590 nm, A = 0.138 A = cl 0.138 = x 0.002M x 1 cm = 0.138/ 0.002 x 1 = 69 M-1 cm-1

0.2

0.15 0.1 0.05 0

300 350 400 450 500 550 600 650 700 Wavelength (nm)

Transitions allowed by the selection rules (high values > 1000 M-1cm-1).

Laporte Selection Rule

Transitions between d-orbitals (g) forbidden by the Laporte selection rule

Octahedral complexes Centrosymmetric: t2g and eg orbitals

Selection rule lifted by molecular vibration

s-orbital gerade

d-orbital gerade

p-orbital ungerade

Tetrahedral complexes non-Centrosymmetric: t2 and e orbitals

e.g.

p-orbital to d-orbital d-orbital to d-orbital

by the Laporte selection rule by the Laporte selection rule Tetrahedral complexes are usually more strongly coloured than analogous octahedral complexes

The Spin Selection Rule

Assumptions made in CFT 1. 2. Explains 1. 2. 3. Geometry Magnetism Colour The ligands are Interactions are purely

Limitations Does not allow for in M-L bonding

Doesn't explain Order of ligands in the Spectrochemical Series Nephelauxetic Effect

The Spectrochemical Series Weak Field Ligands High Spin Complexes Strong Field Ligands Low Spin Complexes "there is

The Nephelauxetic Effect

in complexes than in the free ion"

- some I- < Br- < S2- < SCN- < Cl-< NO3- < F- < OH- < ox2- < H2O < NCS- < CH3CN < NH3 < en < bpy < phen < NO2- < phosph < CN- < CO

in M-L bonds M and L share electrons

- effective size of metal orbitals - electron-electron repulsion

Nephelauxetic series of ligands F- < H2O < NH3 < en < [oxalate]2- < [NCS]- < Cl- < Br- < ICFT does not explain why some ligands with charges are than analogous ligands which are not charged Nephelauxetic series of metal ions Mn(II) < Ni(II) Co(II) < Mo(II) > Re (IV) < Fe(III) < Ir(III) < Co(III) < Mn(IV)

LFSE:the EXTRA stabilisation of complexes that occurs as a result of the splitting of orbitals in a ligand field (cf. to CFSE: it is always positive and no account of P is taken) LFSE Octahedral (always greater than tetrahedral) high/low spin options d4 to d7 only
d1 d2 d3 3/5o -2/5O

eg t2g

d1 : LFSE 0.4 d2 : LFSE 0.4 X 2 = 0.8 d3 : LFSE 0.4 x 3 = 1.2 maximum d4 hs : LFSE 0.4 x 3 0.6 = 0.6 d4 ls : LFSE 0.4 x 4 = 1.6

d4 eg

d4

d5

d5 3/5o -2/5O

d5 hs : LFSE 0.4 x 3 0.6 x 2 = 0 minimum d5 ls : LFSE 0.4 x 5 = 2.0 highest d6 hs : LFSE 0.4 x 4 - 0.6 x 2 = 0.4 d6 ls : LFSE 0.4 x 6 = 2.4

LFT is identical to CFT, except that it allows for some parameters.

in M-L bonding.

t2g

d6 eg

d6

LFT is based on

d7

d7 3/5o -2/5O

d7 hs : LFSE 0.4 x 5 0.6 x 2 = 0.8 d7 ls : LFSE 0.4 x 6 0.6 = 1.8 d8 : LFSE 0.4 x 6 0.6 x 2 = 1.2 maximum

t2g

ls gives higher LFSE than hs option

Variation in LFSE with excluding P)

Lattice Energies (from Born Haber cycle) For 1st row M(II) chlorides: hs, Oh

Ca(II)

Ti(II)

V(II)

Cr(II).etc

ls d6: hs d0, d5, d10 : hs Oh d3, d8 :

LFSE LFSE LFSE

The energy separation to form a crystal Mn+(g) + n X-(g)

when ions come together from infinite

MXn(s)

Discrepancies in lattice energies are a result of

Variation in Hydration Enthalpies

Enthalpy of hydration: M2+(g) + xs H2O [M(OH2)6]2+(aq)

Variation in Ionic Radii

Ca2+
high spin low spin

Zn2+

Last Lecture 9 lecture course on Coordination Chemistry Prof. Sylvia Draper

Sc3+
high spin

Ga3+

So. CFSE, LFE and MO theory agree ! - each one building upon and improving the other

low spin

low spin: steady high spin: steady

followed by increase from t2g6 eg1 followed by increase from t2g3 eg1

Ionisation Energies of first row TM ions, hs, Oh

Irving-Williams series

[M(H2O)6]2+

[EDTA]4-

[M(EDTA)]2- +

6H2O

Position of equilibrium depends on

d5

d6

d7

d8

d9

d10

Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ > Zn2+

Valance Bond Theory Ligand = Lewis base Metal = Lewis acid s, p and d orbitals give with specific geometries Number and type of M-L hybrid orbitals determines geometry of the complex

Tetrahedral e.g. [Zn(OH)4]2-

Square Planar e.g. [Ni(CN)4]2-

Octahedral Complex e.g. [Cr(NH3)6]3+ Limitations of VB theory Assumes bonding is Does not account for Can predict Does not account for wrongly

Molecular Orbital (MO) theory MO theory considers covalent interactions e.g. molecular hydrogen Linear Combination of Atomic Orbitals (LCAO)

Ligand Group Orbitals Metal valance shell orbitals = Ligand valance shell orbitals =

LCAO approach

e.g. [Co(NH3)6]3+ = sigma-bonded complex 1s 2s 2p

1s

1s

zz

sp3

hybrid orbitals

N H H H

H atom

H2 molecule

H atom

Six sp3 hybrid ligand orbitals form a set of

e.g. [CoF6]3-

t1u*

Co3+ = 6 e6 x F- = 12 e-

Complexes with M-L -bonding e.g. H2O,OH-, lower halides Cl-, Br-, Ielectron density to the metal centre ligand orbital and metal orbital of electron density from filled p orbitals -bond -bond -bond

a1g*

Total = high spin

4p 4s eg* 3d t2g 6 x LGO eg t1u

L

-acceptor ligands e.g. CO, N2, NO, alkenes electron density from the metal centre metal orbital and ligand orbitals O C O

Mn+

a1g ML6n+

L L L

L L

of electron density into emtpy -antibonding orbitals

-donor ligands: filled ligand orbitals and empty metal orbitals t1u* a1g* eg* Ligand -orbitals (occupied) 3d Ligand -orbitals (occupied) eg Metal d electrons (d6 example) t1u a1g Energy Mn+ ML6n+ 6L small oct - weak field ligand

-acceptor ligands: back-donation to empty ligand antibonding orbitals t1u* a1g* large oct - strong field ligand Ligand -orbitals 4p 4s 3d Ligand -orbitals (occupied) Metal d electrons (d6 example) eg t1u a1g Energy Mn+ ML6n+ 6L eg* (vacant)

4p 4s