4th EucheMs chemistry congress

Poster Session 1
s941
chem. Listy 106, s587–s1425 (2012)
Poster session 1 - inorganic Chemistry
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hiGhLy SeLeCtive Pd-CAtALyzed
heCK CouPLinG reACtionS uSinG A
PhoSPhoruS-nitroGen ContAininG LiGAnd
M. JoShAGhAni 1 , S. JAMALi 2 , e. rAfiee 1 , A. AtAee 1 ,
S. nAdri 1
1 Razi University, Chemistry, Kermanshah, Iran
2 Sharif University of Technology, Chemistry, Tehran, Iran
Phosphorus–nitrogen containing ligands have particular use
in catalysis where it is necessary for a part of ligand to dissociate
and allow an organic fragment to coordinate and undergo
transformations. [1–2] They have interesting dual characteristics;
they coordinate metal ions by phosphorous and/or nitrogen sites
depend on the hard-soft nature of the metal ion and the same time,
the nitrogen atoms act as base whenever a base is required in the
reaction. Among them, 2,6-bis(diphenylphosphino)pyridine
(bdppp, (Ph P) Py) is an unique P-N ligand with rigid and
2 2
relatively large bite angle. This rigidity governs the P...N...P bite
distance so that binding a metal to each donor site places the metal
ions in very close proximity (about 2.6-2.8 ?). In the other hand,
the rigidity of phosphine ligand is very important in selective
Pd/phosphine-catalyzed cross-coupling reactions. Therefore, in
continuation of our previous study on cross-coupling reactions, [3–4]
we encourage to study the Pd-catalyzed heck coupling reactions.
A series of aryl bromides containing electron withdrawing
and/or electron donating groups were sufficiently used for
aryaltion of styrene.
references:
1. A. Zapf, M. Beller, Chem. Commun. 2005, 431.
2. P. Bhattacharyya, J.D. Woollins, Polyhedron 14, 1995,
3367.
3. Sh. Nadri, E. Azadi, A. Ataei, M. Joshaghani, E. Rafiee,
J. Organomet. Chem. 2011, 696, 2966-2970.
4. Sh. Nadri, M. Joshaghani, E. Rafiee, Organometallics
2009, 28, 6281–6287.
Keywords: Heck Reaction; Cross Coupling; Palladiujm;
Phosphine;
4 th EucheMs chemistry congress
P - 0 1 6 1
CyCLen And CroSS-BridGed CyCLen
derivAtiveS trAnS-n-diSuBStituted for
CoPPer(ii) CoMPLexAtion
C. v. eSteveS 1 , L. M. P. LiMA 1 , P. MAteuS 1 ,
r. deLGAdo 1
1 Instituto de Tecnologia Química e Biológica Universidade
Nova de Lisboa, Chemistry, Oeiras, Portugal
Tetraazamacrocycles such as cyclen (1,4,7,10-tetraazacyclo -
dodecane) and their N-functionalized derivatives continue to
interest many scientists owing to their ability to form very
stable metal complexes. [1] In particular, cross-bridged
tetraazacycloalkanes are proton sponges and their increased
structural rigidity lead to kinetically inert metal complexes, making
them interesting candidates for applications such as positron
emission tomography (PET) (using 64Cu-labelled macrocycles) or
radiotherapy (with 67Cu-labelled macrocycles). [2, 3]
In this work two different types of cyclen derivatives were
synthesized, with or without a cross-bridge, exploring different
methylphenol-based pendant arms in search for enhanced
copper(II) coordination ability. The cross-bridged cyclen
derivatives were studied comparatively with the non cross-bridged
ones regarding their acid-base and complexation behaviour.
Copper(II) complexes were studied in solution and in solid state
by a range of potentiometric, spectroscopic and crystallographic
techniques.
Acknowledgements: The authors acknowledge Fundacio para a
Ciencia e a Tecnologia with co-participation of the European
Community fund FEDER, POCI, QREN and COMPETE,
for the financial support under Project PTDC/QUI/67175/2006.
The authors also acknowledge P. Brand and V. Félix for the
crystal structures determination.
references:
1. Delgado, R.; Félix, V.; Lima, L. M. P.; Price, D. W.;
Dalton Trans. 2007, 2734-2745.
2. Bernier, N.; Costa, J.; Delgado, R.; Félix, V.; Royal, G.;
Tripier, R.; Dalton Trans. 2011, 40, 4514-4526.
3. Wadas, T. J.; Wong, E. H; Weisman, G. R.; Anderson, C. J.;
Chem. Rev. 2010, 110, 2858-2902.
Keywords: Macrocyclic ligands; Cyclen; Cross-bridged
cyclen; Copper Complexes;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc