Research
projects at ICCOM
C-C BOND FORMING REACTIONS IN WATER
Ph.D. position (shared with UAL),
starting date July 2006
Olefin metathesis is a catalytic process in which alkenes are
transformed into new products by rupture and reconstruction of
carbon-carbon double bonds. The fundamental features of the process
bring it forward in the world scenery of advanced chemical research,
which is addressed to develop selective and clean processes, in light
of the environmental constraints which have become more and more
rigorous.
During last decade, the opportunities to use olefin metathesis in
synthetic organic chemistry have grown enormously, due to the
introduction of well defined and functional-group-tolerant catalysts
exemplified by the Grubbs catalyst [RuCl2(=CHPh)(PCy3)2]. Current work
in our laboratory is aimed at investigating the catalytic reactions
bringing about alkene metathesis in water as well as exploring the
synthetic scope of highly accessible Ru-based water-soluble
unsaturated carbenes. In this respect, particular attention is being
paid to investigate the tolerability of the process to different polar
functional groups.
The project will suit a Ph.D. candidate working in 18 months in Florence (CNR) and
15 months in Almeria (UAL) and will involve synthesis (UAL) and testing (CNR) of new
water soluble low valent transition metal vinylidenes and allenylidenes
in homogeneous water phase metathesis reactions and related mechanistic
studies.
Requirements: basic expertise in organic and organometallic synthesis,
NMR spectroscopy; GC, GC-MS and HPLC analyses. Knowledge of homogeneous
catalysis is not required but welcome. Envisaged partners: UAL
NOVEL WATER SOLUBLE HIGH VALENT Ru AND Re-OXO COMPLEXES FOR
CATALYTIC OXYGEN TRANSFER
Postdoctoral position, starting date July 2004, duration
6 months - POSITION FILLED IN
The project is destined to a Postdoctoral Fellow and will involve the
synthesis and characterization of new water soluble Ru and Re high
valent oxo complexes for use as homogeneous catalysts in selective
oxygen transfer reactions. Water solubility will be achieved by
choosing the appropriate set of ancillary ligands (mainly N-based)
which will either be synthesized in our group or obtained from the
partner groups within the network. The complexes will be tested for the
activation of H2O2, alkyl hydroperoxides and other stoichiometric
oxidants, to verify the activity on oxygen transfer reactions to
substrates of interest such as organic sulfides and sulfoxides,
benzothiophenes (oxidative HDS), steroids, alkenes and carbohydrates.
Requirements: Ph.D. in organometallic synthesis, expertise in NMR, IR,
UV-vis spectroscopies, GC, GC-MS and HPLC analyses. Knowledge of
homogeneous catalysis is not required but welcome. Envisaged partners:
CNRS-LCC.
References
1) Akbayeva, D.; Gonsalvi, L.; Oberhauser, W.; Peruzzini, M.; Vizza, F.;
Brüggeller, P.; Romerosa, A.; Sava, G.; Bergamo, A.
"Synthesis, catalytic properties and biological activity of new water
soluble ruthenium cyclopentadienyl PTA complexes [(C5R5)Ru(PTA)2Cl]
(R = H, Me; PTA = 1,3,5-triaza-7-phosphaadamantane)", Chem. Commun. 2003, 264-265.
2) Saoud, M.; Romerosa, A.; Peruzzini, M.
"Water Soluble Ruthenium Vinylidene and Allenylidene Complexes:
Potential Catalysts for Ring-Opening Metathesis", Organometallics, 2000,
19, 4005-4007.
3) Saoud, M.; Romerosa, A.; Mañas Carpio, S.; Gonsalvi, L.;
Peruzzini, M.
"Ruthenium-catalysed selective transetherification of substituted vinyl
ethers to acetals and aldehydes", Eur. J. Inorg. Chem., 2003, 1614 - 1619.
4)
Baucherel,
X.; Gonsalvi, L.; Arends, I. W. C. E.; Ellwood, S.; Sheldon, R. A.
"Aerobic
oxidation of cycloalkanes, alcohols and ethylbenzene catalyzed by the novel
carbon radical chain promoter NHS (N-hydroxy saccharin)", Adv.
Synth. Catal.
2004,
346, 286-296.
Cost of living in the Florence/Sesto Fiorentino Area
Accommodation:
- self contained furnished flat, Florence or Sesto, average 600 €/month
excl. bills
- furnished room in a shared flat, from 3 to 4 people, Florence or
Sesto, range 300-400 €/month excl. bills depending on area.
A number of hostels allow temporary accommodation
Other living expenses: around 300 €/month.
Contacts:
Dr. Maurizio Peruzzini and Dr. Luca Gonsalvi
Istituto di Chimica dei Composti Organometallici (ICCOM)
Area di Ricerca del CNR, Via Madonna del Piano
50019 Sesto Fiorentino (Florence), Italy
phone (Q) +39 055 5225 289
mobile +39-328 8163836
fax
+39 055 5225 203
e-mail:
maurizio.peruzzini@iccom.cnr.it
Job application: l.gonsalvi@iccom.cnr.it