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Université de Fribourg

Formation and Reactivity of [(tacn)-N-CO-Re(III)Br(CO)(2)](+) in Water : a Theoretical and Experimental Study

Zobi, Fabio ; Blacque, Olivier ; Steyl, Gideon ; Spingler, Bernhard ; Alberto, Roger

In: Inorganic Chemistry, 2009, vol. 48, no. 11, p. 4963-4970

The chemistry of [(tacn)-N-CO-Re(III)(CO)(2)Br]X (X = Cl or Br), obtained in good yield from the reaction of fac-[(tacn)Re(I)(CO)(3)]Br (1, tacn = 1,4,7- triazacyclononane) with X(2) in water, is described. The [(tacn)-N-CO-Re(III)(CO) (2)Br]X complex (2 with X = Br(-); 2a with X = BrCl(2)(-)), which we have previously communicated, is characterized by an unusual three-membered ring acyl amide...

Université de Fribourg

Ligand electronic parameters as a measure of the polarization of the C≡O bond in [M(CO)(x)L(y)]n complexes and of the relative stabilization of [M(CO)(x)L(y)](n/n+1) species

Zobi, Fabio

In: Inorganic Chemistry, 2010, vol. 49, no. 22, p. 10370-10377

The electronic description of octahedral (fac-[M(CO)(3)L(3)](n), with M = Re, Ru, and Mn, and [Cr(CO)(5)L](n)), square-planar (cis-[Pt(CO)(2)L(2)](n)), and tetrahedral ([Ni(CO)(3)L](n)) carbonyl complexes (where L = monodentate ligand) was obtained via density functional theory and natural population analyses in order to understand what effects are probed in these species by vibrational...

Université de Fribourg

Synthesis and reactivity of the 17 e- complex [Re(II)Br4(CO)2]2 : A convenient entry into rhenium(II) chemistry

Zobi, Fabio ; Kromer, Lukas ; Spingler, Bernhard ; Alberto, Roger

In: Inorganic Chemistry, 2009, vol. 48, no. 18, p. 8965-8970

The reduction of (Et(4)N)[Re(III)Br(4)(CO)(2)] (1) by 0.5 equiv of tetrakis- dimethylaminoethylene in acetonitrile yields directly the air-stable, 17-electron Re(II) synthon (Et(4)N)(2)[Re(II)Br(4)(CO)(2)] (2) in nearly quantitative yield. The versatility of 2 as a synthon for Re(II) chemistry was demonstrated by substitution reactions of [Re(II)Br(4)(CO)(2)](2-) with different mono-, bi-,...

Université de Fribourg

Aerobically stable and substitutionally labile α-diimine rhenium dicarbonyl complexes

Schindler, Kevin ; Crochet, Aurélien ; Zobi, Fabio

In: RSC Advances, 2021, vol. 11, p. 7511-7520

New synthetic routes to aerobically stable and substitutionally labile α-diimine rhenium(I) dicarbonyl complexes are described. The molecules are prepared in high yield from the cis–cis–trans-[Re(CO)2(tBu2bpy)Br2]− anion (2, where tBu2bpy is 4,4′- di-tert-butyl-2,2′-bipyridine), which can be isolated from the one electron reduction of the corresponding 17-electron complex (1)....

Université de Fribourg

Cytotoxicity of Mn-based photoCORMs of ethynyl-α-diimine ligands against different cancer cell lines: The key role of CO-depleted metal fragments

Rossier, Jeremie ; Delasoie, Joachim ; Haeni, Laetitia ; Hauser, Daniel ; Rothen-Rutishauser, Barbara ; Zobi, Fabio

In: Journal of Inorganic Biochemistry, 2020, vol. 209, p. 111122

A series of tricarbonyl manganese complexes bearing 4-ethynyl-2,2′-bipyridine and 5- ethynyl-1,10-phenanthroline α-diimine ligands were synthetized, characterized and conjugated to vitamin B12, previously used as a vector for drug delivery, to take advantage of its water solubility and specificity toward cancer cells. The compounds act as photoactivatable carbon monoxide-releasing molecules...

Université de Fribourg

Tautomerism and self-association in the solution of new pinene-bipyridine and pinene-phenanthroline derivatives

Solea, Atena B. ; Cornu, Ivan ; Deneva, Vera ; Crochet, Aurélien ; Fromm, Katharina M. ; Antonov, Liudmil ; Allemann, Christophe ; Mamula, Olimpia

In: Molecules, 2020, vol. 25, no. 2, p. 298

Two novel pinene-type ligands have been synthesized and their tautomeric and self- associating behavior studied in solution and in the solid state. The first ligand, an acetylated derivative of 5,6-pinene-bipyridine, displays keto-enol tautomerism in solution. This tautomeric equilibrium was studied by NMR and UV-Vis spectroscopy in various solvents, and the results were compared with the ones...

Université de Fribourg

Different coordination abilities of 1,7- and 4,7-phenanthroline in the reactions with copper(II) salts: Structural characterization and biological evaluation of the reaction products

Stevanović, Nevena Lj. ; Andrejević, Tina P. ; Crochet, Aurélien ; Ilic-Tomic, Tatjana ; Drašković, Nenad S. ; Nikodinovic-Runic, Jasmina ; Fromm, Katharina M. ; Djuran, Miloš I. ; Glišić, Biljana Đ.

In: Polyhedron, 2019, vol. 173, p. 114112

The reactions between equimolar amounts of CuX2 (X = NO3− and CF3SO3−) and two aromatic nitrogen-containing heterocycles differing in the position of nitrogen atoms, 1,7- and 4,7-phenanthroline (1,7- and 4,7-phen), were performed in ethanol/methanol at room temperature. When CuX2 salts were mixed with 4,7-phen, two copper(II) complexes, [Cu(NO3)2(4,7-Hphen)2](NO3)2 (1) and...

Université de Fribourg

Synthesis and structural analysis of polynuclear silver(I) complexes with 4,7-phenanthroline

Stanojević, Ivana M. ; Savić, Nada D. ; Crochet, Aurélien ; Fromm, Katharina M. ; Đuran, Miloš I. ; Glišić, Biljana Đ.

In: Journal of the Serbian Chemical Society, 2019, vol. 84, no. 7, p. 689–699

New polynuclear silver(I) complexes, [Ag(CF3SO3)(4,7-phen)(CH3CN)]n (1) and [Ag(PO2F2)(4,7-phen)]n (2), were synthesized by the reaction of 4,7-phenanthroline (4,7-phen) and the corresponding AgX salt (X = CF3SO3 - and PF6 -) in 1:2 mole ratio, respectively, in methanol/acetone (1:1 volume ratio) at room temperature. The characterization of the complexes was established on the basis of...

Université de Fribourg

Novel iron tweezers complexes for hydrogenation and polymerization of olefins

Mafua, Roger ; Jenny, Titus A. (Dir.)

Thèse de doctorat : Université de Fribourg, 2006 ; no. 1503.

The use of organometallic complexes as catalysts became a very significant topic in the field of material chemistry. However, despite of this development, only few of them contain iron(II), except the tridentate complex diimine pyridine developed by Gibson and Brookhart and employed in the olefin polymerization. Unfortunately, this model suffers by its lack of tolerance towards the minor changes...