aqueous
organometallic catalysis:
The
use of carbon dioxide as c1 building block
In
this program, the group will mainly develop the following project:
Carbon dioxide is an abundant greenhouse gas which could be an important
C1 building block provided its catalytic fixation into larger organic molecules
could be widely realized in synthetic systems. However, in most cases,
hydrogenation of CO2 provides formic acid or its salts, although examples
of hydroformylation of olefins, formylation of N-heterocycles and formation of
lactones in the reaction of dienes with CO2/H2 mixtures are known. Based on our experience on CO2 hydrogenation with Rh- and Ru-phosphine-type catalysts we wish to
catalyze the incorporation of carbon dioxide into olefins in aqueous solutions
or in aqueous-organic biphasic systems. An integrated part of the project
involves the synthesis of new water-soluble transition metal complexes, their
structural characterization (IR, NMR, MS, single crystal X-Ray, etc.) and the
determination of their acid-base properties by pH-potentiometry. In this research
we also plan to study catalysts formed by the new hydrosoluble ligands
developed by our partners. Experience in inorganic/organometallic synthesis
and/or catalysis is desirable.
References:
1. F. Joó, J. Kovács, A.Cs. Bényei, L.
Nádasdi, G. Laurenczy: The effect of pH
on the reactions of catalytically important Rh(I) complexes in aqueous
solution: Reaction of [RhCl(TPPMS)3] and trans-[RhCl(CO)(TPPMS)2]
with Hydrogen (TPPMS=mono-sulfonated triphenylphosphine), Chem.
Eur. J. 2001, 7,
193-199.
2. G. Laurenczy, F. Joó, L. Nádasdi:
Formation and Characterization of Water - Soluble Hydrido-Ruthenium(II)
Complexes of 1,3,5-Triaza-7-phosphaadamantane
and their Catalytic Activity in Hydrogenation of CO2 and HCO3-
in Aqueous Solutions, Inorg. Chem. 2000, 39, 5083-5088.
3. J. Elek, L. Nádasdi, G. Papp, G.
Laurenczy, F. Joó: Homogeneous hydrogenation of carbon dioxide and bicarbonate
in aqueous solution catalyzed by water-soluble ruthenium(II) phosphine
complexes, Appl. Catal. A.: General 2003,
255, 59-67.
4. G. Kovács, L.
Nádasdi, G. Laurenczy, F. Joó: Aqueous organometallic catalysis. Isotope
exchange reactions in H2-D2O and D2-H2O
systems catalyzed by water-soluble Rh- and Ru-phosphine complexes, Green Chem. 2003, 5, 213-217.
The local currency
is Hungarian Forint (HUF); 1 euro equals approximately 260 HUF
(rate of early
February, 2004; please check the actual rate).
·
Accommodation:
- self contained furnished flat, average 60000 HUF/month excl. bills
- furnished room in a shared flat, from 3 to 4 people, range
15000-20000 HUF/month excl. bills depending on area.
Several hostels allow temporary accommodation
Other living expenses
Around 85000 HUF/month.
Contacts:
Institute of
Physical Chemistry, University of Debrecen
1, Egyetem tér,
Debrecen, Hungary
mail: Debrecen 10, P.O.Box 7, H-4010 Hungary
phone :+36
52 512900, ext. 2382 (F.J.) or ext. 2383 (Á.K.)
fax:
+36 52 512915
e-mail: jooferenc@tigris.klte.hu / katho@tigris.klte.hu