4th EucheMs chemistry congress

Poster Session 1
s971
chem. Listy 106, s587–s1425 (2012)
Poster session 1 - inorganic Chemistry
P - 0 2 2 0
new fe(ii) PinCer hydride CoMPLexeS And
their APPLiCAtion in hydroGenAtion
reACtionS
B. BiChLer 1 , K. Mereiter 2 , K. KirChner 1
1 Institute of Applied Synthetic Chemistry, Vienna University of
Technology, Vienna, Austria
2 Institue of Chemical Technology and Analytic, Vienna
University of Technology, Vienna, Austria
Hydrogenation for reducing ketones to alcohols is a
common and often used reaction in modern synthetic organic
chemistry. Particularly the stereoselective synthesis of enantiopure
alcohols is an important topic and usually catalysts based on
precious metals, like ruthenium, iridium or rhodium are used. Well
defined iron complexes with similar reactivity would provide an
excellent alternative, due to the high natural abundance, low costs
and low toxicity.
We here report the synthesis, characterization and reactivity
of Fe(II) Complexes and their application in hydrogenation
reactions. The complexes are based on PNP pincer type ligands
with a pyridine or pyrimidine ring with a P-N bond. [1] All ligands
are accessible in modular fashion based on simple synthetic
methodologies. A useful feature of these ligands is that steric,
electronic, and even stereochemical parameters can be
manipulated by modifications of the phosphino R groups and the
substituents at the aromatic backbone in order to control the
reactivity at the metal center.
The ligands are reacted with FeX (X=Cl, Br) in the
2
presence of CO and a silver salt to get a bis-CO PNP precatalyst
of the type [Fe(PNP)(CO) Cl] 2 + . The CO co-ligand is essential in
order to keep the iron center in a low-spin state throughout the
catalytic cycle as revealed by DFT calculations. Reduction with
elemental Zn yields the catalytic active mono-hydride species.
references:
1. D. Benito-Garagorri, K. Kirchner, Acc. Chem. Res. 2008,
41, 201 - 213.
Keywords: homogeneous catalysis; hydrogenation; iron;
Density functional calculations;
4 th EucheMs chemistry congress
P - 0 2 2 1
SyntheSiS And ChArACterizAtion of noveL
wAter SoLuBLe PhthALoCyAnineS BeArinG
trifLuoroMethyLquinoLine GrouPS
d. evren 1 , A. KALKAn BurAt 1
1 Istanbul Technical University, Department of Chemistry,
34469, Istanbul, Turkey
Email: evren@itu.edu.tr, kalkanayf@itu.edu.tr
Phthalocyanine (Pc) compounds are a very important class
of organic materials. They possess a conjugated system of
π-electrons and exhibit the ability to chelate metal ions at the
center of the ring. The properties of phthalocyanines are influced
both by the nature of substituents on the ligand and by the nature
of the metal ion in the inner core. Phthalocyanines have found
widespread applications in various areas including printing inks,
catalysts, display devices, chemical sensors, non-linear optical
devices, data storage systems, liquid crystalline charge carriers and
second generation photosensitizers for photodynamic therapy . [1–3]
Recently, fluorinated metallophthalocyanines (MPcs) are
receiving a great deal of attention due to their interesting
electron-transfer and photosensitizing properties. [4]
In the present work, we have synthesized novel water
soluble quarternized metal free,zinc and indium phthalocyanines
including trifluoromethylquinoline substituents on the peripheral
positions. The structure of synthesized complexes were
1 characterized by H-NMR, UV-Vis, FT-IR and Mass
spectroscopic techniques.
references:
1. N. B. McKeown, Phthalocyanine Materials Synthesis,
Structure and Function Cambridge University Press., 1998.
2. C.C. Leznoff, A. B. P. Lever, Phthalocyanines; Properties
and Applications, vol. 1-4, VCH, Weinheim, 1989-1996.
3. A. K. Burat, A. Koca, J. P. Lewtak, D. T. Gryko,
Synthetic Metals, vol. 161 (2011), pp. 1537-1545.
4. A. K. Burat, Z.P. Öz, Z. A. Bayir, Monatshefte für Chemie,
vol. 143, (2012), pp. 437-442.
Keywords: Phthalocyanines; Indium; Zinc; Solubility;
Quinoline;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc