Beruflich Dokumente
Kultur Dokumente
CHM 5.33
Fall 2005
Introduction
Refer to:
N2 + 3H2 2NH3
Thermodynamically, the
reaction of N2 with H2 is
Ea
favorable
N2 + 3H2 The problem lies in
overcoming the kinetic barrier
G ~ -4 kcal/mol
2NH3
Image removed due to copyright reasons. Please see: In 2002, Rees reported the 1.6 Å
resolution crystal structure of
Einsle, Oliver et al. "Nitrogenase MoFe-Protein at
1.16 Resolution: A Central Ligand in the FeMo- nitrogenase showing the presence of
Cofactor." Science 297 (2002): 1696-1700. an atom in the center of the FeMo
cofactor
Industrial Production of Ammonia
1918 1931
N2 + 3H2 2NH3
Ti V Cr Mn Fe Co Ni Cu
Zr Nb Mo Tc Ru Rh Pd Ag
O O
O
(acetic anhydride)
NH2
xs.
HN
acetonitrile
O RT, 4h
BF4
M N
Synthesis of Mo[N(t-Bu)Ar]3
(OEt2)Li N
HN
n-BuLi/pentane
MeBu
Mo N
Ho
Ho MeAr
Hp
MeAr
ArRN
NRAr
ArRN
Mo
N
NRAr
ArRN Mo 1 atm N2 N
Mo
pentane, -35oC pentane, 25oC
NRAr N NRAr
ArRN
NRAr
brown Mo
ArRN NRAr orange
NRAr
Experimental purple
Experimentally measured activation J. Am. Chem. Soc., 118, 1996
barrier of 23.3 kcal/mol
Theoretical
No calculated barrier to end-on N2 binding
Calculated activation barrier of 20.8
kcal/mol for break up of the μ-N2 dimer J. Am. Chem. Soc., 117, 1995
Electronic Structure of Mo[t-Bu(Ar)]3
Mo(III) d3
N High spin quartet ground
N Mo
N state
Three fold symmetric (C3v)
t-Butyl groups lie on one
side of the MoN3 face and
aryls on the other sterically
protecting the metal atom
Sigma Bonding
y
z N
The orbitals on Mo
y
N x
that participate in the
N
N
N N
bonding will be s,
x
N dx2-y2, dxy, and to a
N
N
N
smaller extent dz2.
N
N
Pi Bonding Contribution
this combination of
dxy and dx2-y2 also amide p orbitals cannot
participate in bonding with form bonds with the
the p orbitals of the amide metal
ligands
MO Diagram
5e*
4a1* Using ligand field
3a1*
(a1 + e) 5p theory, we can
4e* develop a MO
diagram for the
MoL3 molecule by
(a1) 5s considering how the
3e ligand orbitals
(a1 + e + e) 4d
2a1 transform in C3v
symmetry.
L (a2 + e)
a2
We then consider
the symmetry
2e L (a1 + e) allowed interactions
with the orbitals on
Mo (s, p, and d).
1e
1a1
d-Orbital Configuration
e dxz, dyz
a1 dz2
N
N
N
Isolobal Analogy
2p
2s
Mo N
N2
Mo CH
N N 2p 2p
Mo Mo
HC CH
Roald Hoffmann Nobel Prize
Activation
Mo
ArRN
N
ArRN
5a1*
6e*
4a1*
(a1 + e) 5p
3a1*
5e* -Mo(VI) d 0
(a1) 5s
(a1 + e + e) 4d
4e*
-16e complex
-1 and 2
a2
L ( a2 + e) bonds to N atom
Npx,py (e)
3e L ( a1 + e)
2e
Npz (a1)
1e
2a1
1a1
Thermodynamics
2MoL3 + N 2 2NMoL3
2MoL3 + 2N
MoL3
NH3 0.5 N2
3H
NMoL3
Schrock System
See:
Yandulov, Dmitry V., and Richard R. Schrock. "Reduction of Dinitrogen to Ammonia at a Well-Protected
Reaction Site in a Molybdenum Triamidoamine Complex." J Am Chem Soc 124 (2002): 6252-6253.
See:
Yandulov, Dmitry V., and Richard R. Schrock. "Catalytic Reduction of Dinitrogen to Ammonia at a Single
Conclusions