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Lecture6
Porphyrin
Chlorophyll c2
Heme B
Cobalamin
HN
E helix
O
O
Fe
N
Fe
N
H
N
Proximal Histidine (F8)
F helix
N
H
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
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
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.
M(CO)6
M = Cr/Mo/W
Cr
1x 6
6 CO 6 x 2 = 12
Total number of Valance electron = 18
Mo
= 6 electrons
Benzene (3x2 bond electron) = 6 electrons
3 x CO
=6 electrons
Total number of valance electron = 18
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
trihapto 3
M-M
(2 x 18)
Terminal
carbonyls
Experimentally found structure