University of Puerto Rico at Cayey

Laboratory of Modeling, Simulations and Theory

Building Research Infrastructure and Capacity

Comparative Energetics of Reaction Steps Involved in

Alkane Metathesis on a Silica vs Porous Organic
Polymer Supported Ta-Alkyl Catalyst:
A Computational Study

Xiomaries Torres Garca

Chemistry Department, UPR-Cayey
Dr. Juan M. Lpez Encarnacin
Math-Physics Department, UPR-Cayey
Dr. Julius Jellinek
Chemical Sciences and Engineering Division
Argonne National Laboratory

Global concept of project

Support Synthesis

2C2H6

Metal Incorporation

Application

CH4 +

Metathesis Reactions

Dr. Y. Chauvin

Prof. R. Schrock

Robert H. Grubb

2005: Prof. R. Schrock Massachussets Institute of Technology USA y Dr.

Y. Chauvin Institut Francais du Ptrole France Nobel Prize:
contribution Development of metathesis method in organic synthesis.

Grubbs and his co-workers developed versatile catalysts using Ruthenium

metal.

One of Schrocks molybdenum catalysts

Garca, G.; Herrera, K.; Grillasca, I; Acosta, A. Desarrollo del mtodo de mettesis en sntesis orgnica. Premio Nobel de Qumica. 2006, 39-44.

Metathesis of alkanes and alkenes

Discovered: 1950
Different types of metathesis
Breaking and bond formation of hydrocarbons in a process catalyzed by
certain metal complexes
Convert a hydrocarbon: one carbon atom more or less
The transformation of alkanes to homologs of different chain lengths

Recovered: http://imgkid.com/alkanes-alkenes-alkynes.shtml

Recovered:
http://www.yteach.co.za/index.php/resources/alkenes_isomeri
s_double_bond_reaction_bromine_addition_reaction_hydrog
enation_t_page_6.html

The Nobel Prize in Chemistry 2005 The Royal Swedish Academy of Sciences

The problem
The main problem in any metathesis reactions is the
energy required to form and break the C-H and C-C
bonds. Our test reaction is the conversion of ethane into
propane and methane promoted by a POP-Ta-Alkyl
catalyst.

POP-Ta-Alkyl

2CnH2(n)+2 Cn-iH2(n-i)+2 + Cn+iH2(n+i)+2

Basset, J.; Copret, C.; Soulivong, D.; Taoufik, M.; Cazat, J. Accounts of Chemical Research. 2010, 43, 323-334.

Objectives
General:
Decrease the activation energies of the ethane metathesis as
compare with silica support by using a novel catalyst which
has a porous organic polymer as support
Specifics:
Propose a reaction mechanism for ethane conversion
through a POP-Ta-Alkyl
Propose different organic ligands to mimic the amorphous
POPs and incorporate the Ta-Alkyl complex on it
Design and compute the Gibbs free energies at different
temperatures for molecular models of reactants,
intermediates, transition states, and products involve in the
reaction mechanism for each organic ligand
Build graphs of the reaction energy profile

Justification
Metathesis of alkane and alkenes have large number of
applications, for example:
Obtaining wide variety of molecules
High yields of important pharmaceutical compounds
Reformulation of fuel
Industrial Chemistry
Energetic Aspect
Advantages of porous organic polymers as support of singlemetal reaction centers
Thermal stability
Robust and yet flexible (allowing possible twisting which
help in reducing the energy barriers)
Lpez, J.; Tanabe, K.; Johnson, M.; Jellinek, J. Chem. Eur. J. 2013, 19, 13646-13651.

Proposed Mechanism for Ethane Metathesis

2C2H6

[Ta] Catalyst
g

Molecular Models of Ta-Alkyl (T5)

Catalyst on Different Supports

CH4 + C3H8

Proposed Mechanism

I
POP-P5-O2-T5

II
POP-P2-O2-T5

III
Silica-T5

5
The numbers label reaction steps

IV
POP-P2-(NCH3)2-T5

Molecular ligands proposed as model of the

porous organic polymers
POP-1

POP-1-Extended

Computational Methodology
Design of molecular models

Analysis of the results

Quantum Mechanics
Density Functional Theory
PW91-Exchange and
Correlation Functional

Transfer data from

supercomputer

Support Effects in Ethane Metathesis:

Comparative Energetics
2C2H6

Exothermicity E (eV)

1.4

[Ta] Catalyst
g

CH4 + C3H8

[ Ta ] Catalyst

1.2

1.0
0.8

II

0.6
0.4
0.2

III

0.0
-0.2

IV

-0.4
1

Reaction step
The computations identify catalyst IV as a superior synthetic target. Its primary
difference from the other three catalysts is that it furnishes an N-type
coordination environment to the Ta reaction center instead of an O-type (see the
molecular models in the preceding slide).

Test example: Carbene Hydride Mechanism

Energy
Profile

Molecular
complexes
involved in the
top reaction
mechanism
Basset, J.; Schinzel, S.; Chermette, H.; Copret, C. J. Am. Chem. Soc. 2008, 130, 7984-7987.