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Lecture 18-20
One of the most characteristic chemical properties of these elements is the occurrence of multiple oxidation states. Mn(II) Mn(VI) Mn(VII)
[V(H2O)6]2+
[V(H2O)6]3+
[Cr(NH3)6]3+
[Cr(NH3)5Cl ]2+
Scandium
Titanium
Vanadium
Chromium
Manganese
Iron
Cobalt
Nickel
Copper
Coordination Compounds
A coordination compound typically consists of a complex ion and a counter ion.
A complex ion contains a central metal cation bonded to one or more molecules or ions.
The molecules or ions that surround the metal in a complex ion are called ligands. A ligand has at least one unshared pair of valence electrons C O O N H H H H Cl
22.3
Coordination Compounds
The atom in a ligand that is bound directly to the metal atom is the donor atom. N O H H H H H
The number of donor atoms surrounding the central metal atom in a complex ion is the coordination number. Ligands with: one donor atom two donor atoms three or more donor atoms monodentate bidentate polydentate H2O, NH3, Clethylenediamine EDTA
Coordination Compounds
bidentate ligand polydentate ligand (EDTA)
H2N
CH2
CH2
NH2
What are the oxidation numbers of the metals in K[Au(OH)4] and [Cr(NH3)6](NO3)3 ? OH- has charge of -1 K+ has charge of +1 ? Au + 1 + 4x(-1) = 0
Au = +3 NO3- has charge of -1
The names of anionic ligands end with the letter o. Neutral ligands are usually called by the name of the molecule. The exceptions are H2O (aqua), CO (carbonyl), and NH3 (ammine).
When several ligands of a particular kind are present, the Greek prefixes di-, tri-, tetra-, penta-, and hexa- are used to indicate the number. If the ligand contains a Greek prefix, use the prefixes bis, tris, and tetrakis to indicate the number. The oxidation number of the metal is written in Roman numerals following the name of the metal. If the complex is an anion, its name ends in ate.
22.3
Crystal-Field Theory
Model explaining bonding for transition metal complexes
Originally developed to explain properties for crystalline material Basic idea: Electrostatic interaction between lone-pair electrons
result in coordination.
Energetics
CFT - Electrostatic between metal ion and donor atom
i) Separate metal and ligand high energy ii) Coordinated Metal - ligand stabilized iii) Destabilization due to ligand -d electron repulsion iv) Splitting due to octahedral field.
ii
iv iii
d-orbitals not pointing directly at axis are least affected (stabilized) by electrostatic interaction
Ligand-Metal Interaction
Crystal Field Theory - Describes bonding in Metal Complexes
Basic Assumption in CFT: Electrostatic interaction between ligand and metal
d-orbitals align along the octahedral axis will be affected the most. More directly the ligand attacks the metal orbital, the higher the the energy of the d-orbital. In an octahedral field the degeneracy of the five d-orbitals is lifted
The dz2 and dx2y2 orbitals lie on the same axes as negative charges.
Therefore, there is a large, unfavorable interaction between ligand (-) orbitals. These orbitals form the degenerate high energy pair of energy levels. The dxy , dyx and dxz orbitals bisect the negative charges. Therefore, there is a smaller repulsion between ligand & metal for these orbitals.
o
2/5 o
t2g
Strong field
Weak field
Strong field
Weak field
increases with increasing formal charge on the metal ion increases on going down the periodic table
I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO
WEAKER FIELD
SMALLER LONGER
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Weak field
Strong field
Weak field d2
d3
d4
When the 4th electron is assigned it will either go into the higher energy eg orbital at an energy cost of 0 or be paired at an energy cost of P, the pairing energy. d4 Strong field = Low spin (2 unpaired) Weak field = High spin (4 unpaired)
P < o P > o Notes: the pairing energy, P, is made up of two parts. 1) Coulombic repulsion energy caused by having two electrons in same orbital
Pairing Energy, P
The pairing energy, P, is made up of two parts. 1) Coulombic repulsion energy caused by having two electrons in same orbital. Destabilizing energy contribution of Pc for each doubly occupied orbital.
2) Exchange stabilizing energy for each pair of electrons having the same spin and same energy. Stabilizing contribution of Pe for each pair having same spin and same energy
P = sum of all Pc and Pe interactions
1 u.e.
5 u.e.
0 u.e.
4 u.e.
1 u.e.
3 u.e.
d8
d9
d10
2 u.e.
2 u.e.
1 u.e.
1 u.e.
0 u.e.
0 u.e.
To sum up
Electron Configuration for Octahedral complexes of metal ion having d1 to d10 configuration [M(H2O)6]+n.
Only the d4 through d7 cases have both high-spin and low spin configuration.
Electron configurations for octahedral complexes of metal ions having from d1 to d10 configurations. Only the d4 through d7 cases have both high-spin and low-spin configurations.
t
e
t = 4/9o
Always weak field (high spin)
L L M L L L L L M L L L
dx2-y2 dxy
Square planar
M
dxzdyz
Mostly d8 (Majority Low spin) Strong field ligands i.e., Pd2+, Pt2+, Ir+, Au3+
E = hn
22.5
The absorption maximum for the complex ion [Co(NH3)6]3+ occurs at 470 nm. What is the color of the complex and what is the crystal field splitting in kJ/mol?
hc (6.63 x 10-34 J s) x (3.00 x 108 m s-1) = hn= = = 4.23 x 10-19 J 470 x 10-9 m
(kJ/mol) = 4.23 x 10-19 J/atom x 6.022 x 1023 atoms/mol = 255 kJ/mol
22.5
3+ Co
of Color of Light Color of Complex The Wavelength Colors of Some Complexes light absorbed Absorbed 3+ 3+ the 700 Co [CoF6]of (nm) Ion Red Green 600, 420 600, 400 475, 340 470, 340 310 Yellow, violet Yellow, violet Blue, violet Blue, ultraviolet Ultraviolet Dark green Blue-green Yellow-orange Yellow-orange Pale Yellow
The complex with fluoride ion, [CoF6]3+ , is high spin and has one absorption band. The other complexes are low spin and have two absorption bands. In all but one case, one of these absorptionsis in the visible region of the spectrum. The wavelengths refer to the center of that absorption band.
650
580
800
560
Artist color wheel showing the colors which are complementary to one another and the wavelength range of each color.
400
430
490
[Fe(H2O)6
]3+
[Ni(H2O)6]2+
[Co(H2O)6]2+
[Zn(H2O)6]2+ [Cu(H2O)6]2+
If a sample absorbs all wavelength of visible light, none reaches our eyes from that sample. Consequently, it appears black.
If the sample absorbs all but orange, the sample appears orange.
Further, we also perceive orange color when visible light of all colors except blue strikes our eyes. In a complementary fashion, if the sample absorbed only orange, it would appear blue; blue and orange are said to be complementary colors.
650
750 400
580
560
430
490
Chlorophyll a & b
Chl a has a methyl group Chl b has a carbonyl group
Phytol tail