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Profiling an Optimal Pt(II) Based Methane Activation Catalyst by Density Functional Theory. Hongjuan Zhu, Tom Ziegler Department of Chemistry University of Calgary May 28, 2008. Methane Activation. Energy-intensive, two-step process. Direct oxidation process. - PowerPoint PPT Presentation
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Profiling an Optimal Pt(II) Based Methane Activation Catalyst by Density Functional Theory
Hongjuan Zhu, Tom Ziegler
Department of Chemistry
University of Calgary
May 28, 2008
Methane Activation
CH4(g) + H2O(g) CO(g) + 3H2(g)[Ni]
CO(g) + 2H2(g) CH3OH(g)[Cu/ZnO]
Energy-intensive, two-step process
Direct oxidation process CH4(g) + 1/ 2O2
CH3OH(l)
S. S. Stahl, J. A. Labinger, J. E. Bercaw, Angew. Chem. Int. Ed. 1998, 37, 2180
Shilov Reactions
Aleksandre Evgen’yevich Shilov
PtCl42-
RH + D+ RD + H+
PtCl42-
H2ORCH2OH (RCH2Cl) + PtCl4
2-+2HClRCH3 + PtCl62- + H2O (Cl-)
Improve catalyst efficiency?
N. F. Gol’dshleger, M. B. Tyabin, A. E. Shilov, A. A. Shteinman, Zh. Fiz. Khim. (Engl. Transl.) 1969, 43, 1222N. F. Gol’dshleger, V. V. Es’kova, A. E. Shilov, A. A. Shteinman, Zh. Fiz. Khim. (Engl. Transl.) 1972, 46, 785
PtTX2LCH4 + D+ CH3D + H+
X1
X1
CH3
IV
H
Pt
T
T
X2
CH3
X1
X1
II
II
H
Pt
Pt
T
T
X2
PtCH3X2
IV
DX2
D
CH3
X1
X1
L
L
II
II
Pt
Pt
T
T
X2
X2
+ CH4
- L
+ D+
+ CH3D+ L
- H+
N. F. Gol’dshleger, M. B. Tyabin, A. E. Shilov, A. A. Shteinman, Zh. Fiz. Khim. (Engl. Transl.) 1969, 43, 1222
Outline
Determining factor for the energy barrier of methane coordination
Determining factor for the energy barrier of C-H bond cleavage
How to balance the two energy barriers to obtain optimal Pt(II) catalyst
Methane Coordination
Pt
Pt
Pt CH4
TS(1-2)
+ CH4
+ H2O
1
2
ΔG12#
Cl
Cl
Cl
Cl
Cl
Cl
T
T
CH4
H2O
H2O
T
T ΔG12#
(kcal/mol)
F 31.3
Cl 23.3
Br 23.4
I 22.0
NO2 20.9
CN 24.9
H. Zhu, T. Ziegler, Organometallics 2007, 26, 2277H. Zhu, T. Ziegler, J. Organomet. Chem. 2006, 691, 4486
Methane Coordination
Pt
Cl
ClT
CH4
OH2
Geometry of TS(1-2)
T Pt-C (Å) Pt-O (Å)
F 2.88 2.88
Cl 2.97 2.89
Br 2.99 2.89
I 3.01 2.97
NO2 3.00 3.02
CN 3.00 3.03
Methane Coordination
Pt
Pt
Pt CH4
TS(1-2)
+ CH4
+ H2O
1
2
ΔG12#
Cl
Cl
Cl
Cl
Cl
Cl
T
T
CH4
H2O
H2O
T
F < Cl < Br < I < NO2 < CN
trans-directing ability of L
weak strong
F > Cl > Br > I > NO2 > CN
energy barrier of methane coordination
lowhigh
F > Cl > Br > I > NO2 > CN
Pt-CH4 bond strength trans to L
weakstrong
C-H Bond Cleavage
Pt CH4
PtCH3
Pt CH3
TS(2-3)
+ H2O
2
3
ΔG23#
Cl
Cl
T
T H
Cl
Cl
+ H2O
Cl
ClT
H
+ H2O
T ΔG23#
(kcal/mol)
F 0
Cl 1.1
Br 2.1
I 3.6
NO2 16.6
CN 28.6
H. Zhu, T. Ziegler, Organometallics 2007, 26, 2277
H. Zhu, T. Ziegler, Organometallics 2008, in press
C-H Bond Cleavage
Pt
Cl
Cl
CH3
H
T
Pt
Cl
Cl
CH3
H
T
Pt-methane intermediate
Transition State of C-H bond cleavage
T Pt-C (Å) Pt-H (Å)
Intermediate TS Intermediate TS
F 2.27 - 1.63 -
Cl 2.36 2.14 1.72 1.59
Br 2.38 2.13 1.74 1.60
I 2.41 2.05 1.77 1.63
NO2 2.53 1.93 1.85 1.63
CN 2.53 2.15 1.98 1.61
C-H Bond Cleavage
Pt CH4
PtCH3
Pt CH3
TS(2-3)
+ H2O
2
3
ΔG23#
Cl
Cl
T
T H
Cl
Cl
+ H2O
Cl
ClT
H
+ H2O
trans-directing ability
F < Cl < Br < I < NO2 < CN
weak strong
Pt-C bond length in Pt-methane intermediate
F < Cl < Br < I < NO2 < CN
short long
Pt-C bond length in Transition State
F ~ Cl ~ Br ~ I ~ NO2 ~ CN
similar
energy barrier of C-H bond cleavage
F < Cl < Br < I < NO2 < CN
low high
Facilitation of the replacement or substitution of a second ligand trans to the first by an external ligand
trans-directing ability
F < Cl < Br < I < NO2 < CN
weak strong
Trans Effect
Pt
Cl
Cl
TPt
Cl
Cl
T + L (CH4) L (CH4)
electronegativity of T
ligand orbital energy
d-composition in PtCl2T- orbitals
overlap between PtCl2T- and L (or CH4)
R. H. Crabtree, The Organometallic Chemistry of the Transition Metals; Wiley: New York (1998)
Optimal Pt(II) catalyst
Pt
Pt CH4
Pt CH3
TS(1-2)
TS(2-3)
+ CH4
1
2
3
ΔG12#
ΔG23#
T H2O
Cl
Cl
T
Cl
Cl
+ H2OH
TCl
Cl + H2O
Pt Pt CH4 Pt CH3
+ CH4
1 2 3
T H2O
Cl
ClT
Cl
ClH
TCl
Cl- H2O•Trans ligand T affects the two energy barriers in opposite directions
•Too weak or too strong trans ligand T would make one energy barrier dominate.
•Optimal Pt(II) catalyst should have medium trans ligand T because medium T would reduce the first energy barrier while still keep the second one relatively lower
Conclusions
• The determining factor for the energy barriers of both methane coordination and C-H bond activation is the trans ligand T, which changes the two energy barriers in opposite directions
• Optimal Pt(II) catalyst for the Shilov reaction can be obtained by using ligand T with medium trans directing ability