CHM102A
Lecture6
Coordination Complexes in Biological Systems
Porphyrins are heterocyclic macrocycles composed
of four modified interconnected pyrrole subunits.
subunits
They form coordination complexes with metal ions
and are found in biological systems.
Porphyrin
Chlorophyll c2
Heme B
Cobalamin
Hemoglobin and Myoglobin
Hemoglobin
H
l bi (Hb)
MW: 64.5 kDa
Peptide chains: 22
Number of amino acids
: 2x 141
: 2x146
Active site: Fe(II)
Function: cooperatively binds to and transports O2
Myoglobin (Mb)
MW: 17.8
17 8 kDa
Peptide chains:
Number of amino acids
: 161
A ti site:
Active
it Fe(II)
F (II)
Function: binds and transports O2
Notice that the hemoglobin is essentially a tetramer of myoglobin. (There are four
myoglobin like units in hemoglobin.)
3
Hemoglobin and Myoglobin
Oxygenated and Deoxygenated Forms
HN
E helix
Distal Histidine (E7)
N
O
O
Fe
N
Fe
N
H
N
Proximal Histidine (F8)
F helix
Proximal Histidine (F8)
N
H
Crystal field splitting for Square Planar complex
d x2-y 2
dx 2-y 2
dx 2-y 2, dz 2
d z2
d
orbitals
d xy
d xy
dz2
dxy , dyz, d xz
dyz, dxz
Energy
d yz, dxz
Octahedral
complex
Square
pyramidal
Square Planar
complex
6
Coordination Environment of Fe
5 coordinate
Total unpaired electrons = 4, S = 2
Deoxygenated form is high-spin and
paramagnetic
dx2-y2
6 coordinate
Total unpaired electrons = 1, S = 1/2
Oxygenated form is low-spin
The magnetic moment of Fe3+ and the
superoxide
id radical
di l involves
i l
in
i antii
ferromagnetic coupling and the oxygenated
complex is not paramagnetic
dz2
O
O
Fe3+
dxz
dxy
dyz
N
H
Hemoglobin and Myoglobin
Fe-O-O = 150
Raman Spectra gives o-o at 1105 cm-1.indicating that the complex should be in a
superoxide state
o-o (cm-1)
O2
O2
1560
1100
2
O22
850-740
8
The Role of the Protein
Hemoglobin and Myoglobin
Isolated protein free heme model system binds CO 25,000 times stronger
than O2
steric constraints imposed by the amino acid residue on the distal side of the
porphyrin (distal histidine) and by selective hydrogen bonding favoring O2 over
10
CO coordination (less for CO; KCO/KO2 = 200)
Organometallic Chemistry
Organometallic Compounds
In simpler terms these are compounds containing metal-carbon bonds
Examples: CH3-MgBr, Ph-Li, [Ni(CO)4], Ferrocene etc.
These compounds can be seen as having covalent bonds between the metal and the
carbon atom(s).
In general, compounds having a metal
metal-ligand
ligand bond of considerable covalent character
have similar chemistry and follow the chemical behavior of organometallic compounds
Metal-cyano
y
complexes
p
are not considered as organometallic
g
compounds,
p
, while metal
carbonyl complexes are.
Stability of Organometallic Compounds
Compounds
p
with filled octet electrons ((such as CH4, NH3, etc.)) are stable as theyy
attain inert gas configuration (Lewis octet rule, 1916)
Having 18 electrons in the outer shell consisting of s, p and d orbitals is considered
as an indication of stability as in inert gases (Kr (36), Xe (54) or Rn(86).
The rule suggests that compounds that can attain 18 electrons within the bonding
orbitals of the metal show increased stability (Sidwick 1927)
[Co(NH3)6]3+
[Co(
Co3+ 1 x 6 = 6
6 NH3 6 x 2 = 12
Total number of Valance electron = 18
M(CO)6
M = Cr/Mo/W
Cr
1x 6
6 CO 6 x 2 = 12
Total number of Valance electron = 18
Scope of 18-electron Rule
hexahapto 6
?
Mo
= 6 electrons
Benzene (3x2 bond electron) = 6 electrons
3 x CO
=6 electrons
Total number of valance electron = 18
Therefore, this compound is stable
Hapticity: The number of atoms in the ligand which are directly coordinated to the metal.
H ti it is
Hapticity
i denoted
d t d as
pentahapto 5
Neutral atom
W
= 6 electrons
Cp
= 5 electrons
other Cp = 3 electrons
2 x CO = 4 electrons
Total number of valance electron = 18
By oxidation state of metal and ligand
W2+
= 4 electrons
One cyclopentadiene (Cp)
= 6 electrons
other cyclopentadiene (Cp) = 4 electrons
2 x CO
= 4 electrons
Total number of valance electron = 18
Therefore this compound is stable
Therefore,
trihapto 3
Polynuclear metal carbonyls :Scope of 18-electron Rule
Possible to determine number of metal-metal bonds in the carbonyl complexes
Formed to attain the stability through18-electron system.
Let us take example of Mn2(CO)10
2 Mn 2 x 7 = 14
CO 10 x 2 = 20
Total number of Valance electron = 34 / 2 = 17 e- per [Mn(CO)5]
M-M
Therefore total number of Valance electron = 36
(2 x 18)
Experimentally found dimeric structure
Polynuclear Metal carbonyls: Bridging vs terminal
Carbonyl groups can also bridge between two metals
Here CO can be seen as contributing one electron each to the two metals
Try for Fe2(CO)9
Fe 2 x 8 = 16
9 CO 9 x 2 = 18
Total number of Valance electron = 34
M-M
= 2
Therefore total number of Valance electron = 36
Bridged carbonyls between two metals
Terminal
carbonyls
Experimentally found structure
How to find bridging vs terminal carbonyls in a given metal carbonyl complex?
Determined using Infrared spectroscopy (IR) (through one of the factor vibration of bonds)
Bond strength determined using stretching frequency in IR
Greater the bond strength more the stretching frequency
Weaker bond strength in bridged carbonyls resulting less stretching frequency
IR stretching
t t hi frequency:
f
Free carbonyl:
2143 cm-1
Terminal carbonyls:
2125-1850 cm-1
Bridged carbonyls:
1850-1700 cm-1
