Hydroformylation: Proposal
Heterogenizing Tandem Hydroformylation/Hydrogenation Catalysis
Chem 462 Inorganic Chemistry
Dr. Marcetta Y. Darensbourg
Sergio Sanchez and Junsang Cho
12/2 (Tues)
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Contents
I. Background
- hydroformylation reaction
- comparison between homogeneous and heterogeneous catalysts
- strategy for making heterogeneous catalysts
II. Significance
- tandem hydroformylation/hydrogenation protocol and heterogeneous catalysts
- BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) ligands for hydroformylation/hydrogenation
III. Main goal and specific aim of our proposal
- to make a one-pot tandem hydroformylation/hydrogenation in heterogeneous MOFs catalysts
IV. Experimental plan
- modification and designing of the BINAP linker molecules to facilitate the tandem process
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Hydroformylation reaction
- catalyst: bidendtate diphosphine-Rh catalyst used due to high regioselectivity
and conversion yield
- linear aldehyde: used for the production of industrially useful compound of the
linear alcochols
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Homogeneous vs Heterogeneous catalyst
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Why heterogenous catalysts are needed
Reaction place
Rh price
Rh price
Rh price
Rh price
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Strategies for making heterogeneous catalysts
1. Covalent immobilization on
inorganic supports/ polymeric
resin
2. Immobilization by encapsulation
3. Immobilization by electrostatic
interaction
- support-catalysts
- MOFs (metal organic frameworks)
- mesoporous zeolite
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Tandem process of the hydroformylation/hydrogenation
RCH2CH3
Hydroformylation + hydrogenation → linear alcohols
Tandem process must overcome direct hydrogenation of alkene.
Angew. Chem. Int. Ed., 2009, 121, 8166–8170
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BINAP ligand for hydroformylation/hydrogenation
Hydroformylation catalyst (BINAP)
BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)
- versatile ligand for both hydroformylation and
hydrogenation reaction
Hydrogenation catalyst (BINAP)
Journal of Molecular Catalyst A: Chemical, 2001, 174, 119-126
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Organometallics 2007, 26, 5987-5999
Main goal of our proposal
Hypothesis: A one-pot tandem process based on Rh-modified BINAP MOFs
catalysts can facilitate the production of linear alcohols
1. Tandem protocol
- one-step process to produce
linear alcohols
- modification of the BINAP
ligand molecules for
tandem process
2. MOF
- heterogeneous catalyst
(easy separation)
- high absorption of the
syngas
- recyclability
MAIN GOAL: modification of the BINAP ligands to build MOFs in
which the tandem process for the hydroformylation/hydrogenation take
places simultaneously, resulting in linear alcohols
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Specific aim 1 (tandem)
- make the hydroformylation/hydrogenation reaction in an one pot
Angew. Chem. Int. Ed. 2012, 51, 2178 –2182
Specific aim 2 (MOFs)
Salicylaldimine-Based Metal−Organic Framework Enabling Highly Active Olefin
Hydrogenation with Iron and Cobalt Catalysts
J. Am. Chem. Soc. 2014, 136, 13182−13185
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Specific aim 2 (MOFs)
Privileged Phosphine-Based Metal–Organic Frameworks for Broad-Scope Asymmetric
Catalysis
- Rh BINAP based MOF are used for hydrogenation of the alkene
J. Am. Chem. Soc. 2014, 136, 5213−5216
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Design BINAP for tandem process
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Design BINAP for tandem process
1. Primary amine
(n= 1-5)
:only H-bonding is considered and the
effect of number of carbon chain
2. secondary or tertiary amine
(R=H, CH3, Ethyl, t-Butyl; n=1- 5)
: steric bulky effect and nucleophilicity of
amine are taken into account
3. specially designed ligands
: generally used tandem ligands
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Overall goal
Tandem hydroformylation/hydrogenation reaction in Rh-modified BINAP MOFs
(a)
(b)
(c)
Fig. 1. Tandem hydroformylation/hydrogenation catalysts employing Rh-modified BINAP MOFs; (a) MOF
structure, (b) designing of the linker, and (c) tandem process starting from terminal alkene to linear alcohols
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Reaction rate control between the hydroformylation and
hydrogenation
1. Syngas (H2/CO) for the hydroformylation
2. H2 gas only for the hydrogenation
olefin
substrate + catalysts
syngas
(CO/H2)
substrate-catalysts
aldehydes
catalysts-product1
H2 gas
release alcohols
out of the MOFs
catalysts-product2
alcohols
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Conclusions
• In tandem process, hydroformylation/hydrogenation can be
achieved at the same time and place to produce linear
alcohols from terminal 1-alkene.
• Rh-BINAP MOFs can be used as heterogeneous catalysts
with good recyclability.
• Modified BINAP MOFs would be very excellent platform
for the tandem process.
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