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Université de Fribourg

Parametrization of the contribution of mono- and bidentate ligands on the symmetric C[triple bond]O stretching frequency of fac-[Re(CO)(3)](+) complexes

Zobi, Fabio

In: Inorganic Chemistry, 2009, vol. 48, no. 22, p. 10845-10855

A ligand parameter, IR(P)(L), is introduced in order to evaluate the effect that different monodentate and bidentate ligands have on the symmetric C[triple bond]O stretching frequency of octahedral d(6) fac-[Re(CO)(3)L(3)] complexes (L = mono- or bidentate ligand). The parameter is empirically derived by assuming that the electronic effect, or contribution, that any given ligand L will add to...

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

Slow-targeted release of a ruthenium anticancer agent from vitamin B 12 functionalized marine diatom microalgae

Delasoie, Joachim ; Rossier, Jérémie ; Haeni, Laetitia ; Rothen-Rutishauser, Barbara ; Zobi, Fabio

In: Dalton Transactions, 2018, vol. 47, no. 48, p. 17221–17232

Herein we report the synthesis of a new biomaterial designed for targeted delivery of poorly water-soluble inorganic anticancer drugs, with a focus on colorectal cancer. Diatomaceous earth microparticles derived from marine microalgae were coated with vitamin B12 (cyanocobalamin) as a tumor targeting agent and loaded with the well- known anticancer agents cisplatin, 5-fluorouracil (5-FU), and...

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

Correlation of MLCTs of Group 7 fac-[M(CO)3]+ complexes (M = Mn, Re) with bipyridine, pyridinylpyrazine, azopyridine, and pyridin-2-ylmethanimine type ligands for rational photoCORM design

Kottelat, Emmanuel ; Lucarini, Fiorella ; Crochet, Aurélien ; Ruggi, Albert ; Zobi, Fabio

In: European Journal of Inorganic Chemistry, 2019, vol. 2019, no. 33, p. 3758–3768

A mathematical correlation of the MLCT absorption maxima of structurally related fac‐ [M(CO)3L2Br] complexes (M = Mn, Re; L2 = bidentate ligand) is obtained by the comparison of a total of 50 species bearing bipyridine, pyridinylpyrazine, azopyridine and pyridin‐2‐ylmethanimine L2 type ligands. The empirical relationship is first derived by the initial comparison of the MLCT absorption...

Université de Fribourg

Betti bases from 4-(3-pyridazo)-1-naphthol: synthesis, coordination behaviour and unusual substitution reactions

Kurteva, Vanya B. ; Lubenov, Lubomir A. ; Shivachev, Boris L. ; Nikolova, Rositsa P. ; Fromm, Katharina M.

In: ChemistrySelect, 2018, vol. 3, no. 43, p. 12017–12021

A series of Betti bases from 4‐(3‐pyridyl)azo‐1‐naphthol dye, possessing flexible methylene or more constrained aryl‐methyne spaced NH‐containing side‐chains, were obtained and characterized. It was shown by NMR spectroscopy that the ligands exist in keto form. The products’ structure was confirmed by single crystal XRD of a selected sample. A study on the coordination ability...

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.

L’utilisation des complexes organométalliques comme catalyseurs est devenu un domaine très important de la chimie des matériaux. Cependant et malgré ce développement, les catalyseurs à base de fer(II) sont peu employés dans la polymérisation d’oléfines. Un de rares catalyseur utilisé dans ce contexte est le complexe tridenté diimine pyridine développé par Gibson et Brookhart....