Université de Fribourg

New ruthenium(II) complexes with enantiomerically pure bis- and tris(pinene)-fused tridentate ligands: synthesis, characterization and stereoisomeric analysis

Sala, Xavier ; Poater, Albert ; Zelewsky, Alexander von ; Parella, Teodor ; Fontrodona, Xavier ; Romero, Isabel ; Solà, Miquel ; Rodríguez, Montserrat ; Llobet, Antoni

In: Inorganic Chemistry, 2008, vol. 47, no. 18, p. 8016–8024

A new set of Ru−Cl complexes containing either the pinene[5,6]bpea ligand (L1) or the C₃ symmetric pinene[4,5]tpmOMe (L2) tridentate ligand in combination with the bidentate (B) 2,2′-bipyridine (bpy) or 1,2-diphenylphosphinoethane (dppe) with general formula [RuCl(L1 or L2)(B)]⁺ have been prepared and thoroughly characterized. In the solid state, X-ray diffraction...

Université de Fribourg

New synthetic routes toward enantiopure nitrogen donor ligands

Sala, Xavier ; Rodríguez, Anna M. ; Rodríguez, Montserrat ; Romero, Isabel ; Parella, Teodor ; Zelewsky, Alexander von ; Llobet, Antoni ; Benet-Buchholz, Jordi

In: The Journal of Organic Chemistry, 2006, vol. 71, no. 25, p. 9283 -9290

New polypyridylic chiral ligands, having either C₃ or lower symmetry, have been prepared via a de novo construction of the pyridine nucleus by means of Kröhnke methodology in the key step. The chiral moieties of these ligands originate from the monoterpen chiral pool, namely (-)-α-pinene ((-)-14, (-)-15) and (-)-myrtenal ((-)-9, (-)-10). Extension of the...

Université de Fribourg

Stereoselectivity in the formation of tris-diimine complexes of Fe(II), Ru(II), and Os(II) with a C₂-symmetric chiral derivative of 2,2′-bipyridine

Drahoňovský, Dušan ; Knof, Ulrich ; Jungo, Laurence ; Belser, Thomas ; Neels, Antonia ; Labat, Gaël Charles ; Stoeckli-Evans, Helen ; Zelewsky, Alexander von

In: Dalton Transactions, 2006, p. 1444 - 1454

A C₂-symmetric enantiopure 4,5-bis(pinene)-2,2′-bipyridine ligand (–)-L was used to investigate the diastereoselectivity in the formation of [ML₃]²⁺ coordination species (M = Fe(II), Ru(II), Os(II), Zn(II), Cd(II), Cu(II), Ni(II)), and [ML₂Cl₂] (M = Ru(II), Os(II)). The X-ray structures of the [ML₃]²⁺ complexes were determined for Δ-[FeL₃](PF₆)₂,...

Université de Fribourg

Novel HEXOL-type cyclometallated iridium(III) complexes: stereoselective synthesis and structure elucidation

Yang, Liangru ; Zelewsky, Alexander von ; Stoeckli-Evans, Helen

In: Chemical Communications, 2005, vol. (33), p. 4155

Two diastereoisomers of tetranuclear cyclometallated iridium complexes, either having an inner core of HEXOL-type [Ir(IrCl₂)₃]⁶⁺ unit and a surface of six chiral, didentate, cyclometallated ligands, are stereoselectively synthesized from an enantiopure pinenopyridine derivative.

Université de Fribourg

Protonation behaviour of chiral tetradentate polypyridines derived from α-Pinene

Düggeli, Mathias ; Christen, Tobias ; Zelewsky, Alexander von

In: Chemistry - A European Journal, 2005, vol. 11, p. 185-194

Detailed protonation experiments of the [5,6]-pinenebipyridine molecule and the unsubstituted [4,5]- and [5,6]-CHIRAGEN[0] ligands in various solvents indicate a variety of structures of the protonated species. UV-visible and NMR measurements (including ¹⁵N chemical shifts) show the transition from trans to cis conformation of [5,6]-pinenebipyridine upon protonation. The...

Université de Fribourg

Diastereoselective synthesis of coordination compounds: a chiral tripodal ligand based on bipyridine units and its ruthenium(II) and iron(II) complexes

Hamann, Christine ; Zelewsky, Alexander von ; Neels, Antonia ; Stoeckli-Evans, Helen

In: Dalton Transactions, 2004, vol. 3, p. 402-406

The enantiomerically pure chiral tris-chelating ligand (+)-(7S,10R)-L(L) comprising three 4,5-pinenobipyridine subunits connected through a mesityl spacer has been synthesized. Complexes of L with RuII and FeII have been prepared and characterised. NMR spectroscopy indicates that...

Université de Fribourg

Asymmetric Synthesis of Coordination Compounds: Back to the Roots. Diastereoselective Synthesis of Simple Platinum(IV) Complexes

Drahoňovský, Dušan ; Zelewsky, Alexander von

In: Helvetica Chimica Acta, 2005, vol. 88(3), p. 496-506

A publication by Alexander P. Smirnoff in Helvetica Chimica Acta in 1920 [6] describes the first synthesis of a coordination species, i.e., of tris(propane-1,2-diamine-κN¹,κN²)platinum(4+) ([PtIV(pn)₃]⁴⁺), where it was shown that the configuration of a chiral center in the ligand can influence the configuration at the metal. The present investigation of...

Université de Fribourg

Synthesis and Stereochemical Properties of Chiral Square Complexes of Iron(II)

Bark, Thomas ; Zelewsky, Alexander von ; Rappoport, Dmitrij ; Neuburger, Markus ; Schaffner, Silvia ; Lacour, Jérôme ; Jodry, Jonathan

In: Chemistry - A European Journal, 2004, vol. 10(19), p. 4839-4845

Der hexadentate und ditopische Ligand 2,5-Bis([2,2']bipyridin-6-yl)pyrazin bildet bei der Selbstorganisationsreaktion mit Fe²⁺-Ionen einen chiralen, quadratförmigen Tetramerkomplex. Das Racemat dieses Komplexes wurde mit Hilfe von Antimonyltartrat in die Enantiomere getrennt. Die Reinheit des Enantiomers wurde durch NMR-Spektroskopie unter Zuhilfenahme eines chiralen, diamagnetischen...

Université de Fribourg

Complexation behaviour of chiral tetradentate polypyridines derived from α-pinene

Düggeli, Mathias ; Bonte, Christophe ; Zelewsky, Alexander von

In: Inorganica Chimica Acta, 2005, vol. 358(1), p. 41-49

A series of ligands, where two pinene-bipyridine moieties are either connected directly, or through a p-xylene bridge are investigated with respect to their complexation behaviour in solution. The bridged [5,6]-CHIRAGEN[p-xyl] ligands, which are substituted in 5' or 6' positions show self-assembly reactions, which lead to similar supramolecular species as the unsubstituted bis-pinene-bipyridines...