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Therrien, Bruno

Nom
Therrien, Bruno
Affiliation principale
Fonction
Professeur titulaire
Email
bruno.therrien@unine.ch
Identifiants
https://libra.unine.ch/handle/123456789/382
_
0000-0002-0388-2745

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  • Publication
    Métadonnées seulement
    The Goldilocks principle in action: synthesis and structural characterization of a novel {Cu4(?3-OH)4} cubane stabilized by monodentate ligands
    (2013)
    Ardizzoia, G. Attilio
    ;
    Brenna, Stefano
    ;
    Durini, Sara
    ;
    Therrien, Bruno 
    ;
    Trentin, Ivan
    A {Cu4(?3-OH)4} compd., where four Cu(II) and four ?3-bridging O atoms occupy alternate corners of a slightly distorted cube, was prepd. and structurally characterized. This species, formulated as [Cu4(?3-OH)4(Htmpz)8](ClO4)4·1.5Et2O (Htmpz = 3,4,5-1H-trimethyl pyrazole), can be classified as belonging to type I Cu4O4 cubane complexes, and is better described as two CuII-(?-OH)2-CuII units held together by four long Cu-O bonds. The central distorted cubane core is stabilized by neutral monodentate ligands (Htmpz) and perchlorate anions, as demonstrated by single-crystal x-ray structure anal. The title compd. was obtained by hydrolysis of a dinuclear methoxo-bridged species, [Cu(?-OCH3)(Htmpz)2]2(ClO4)2, which was prepd. by reaction of [Cu(Htmpz)4(ClO4)2] with MeOH. All these reactions represent a nice example of the Goldilocks principle in action in coordination chem., since each single actor (solvent, counteranion, and ligand) has the just right electronic, steric or coordinative properties which det. the fate of the final products. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Ruthenium(II) Complexes Bearing a Ligand Derived from P,N- or P,N,O-Diphenylphosphinobenzoxazine: Synthesis, X-ray Characterization, and cis Diastereoselectivity in Styrene Cyclopropanation
    (2012)
    Ardizzoia, G. Attilio
    ;
    Brenna, Stefano
    ;
    Durini, Sara
    ;
    Therrien, Bruno 
    A phosphino-oxazine based ligand (L; 2-(2-(diphenylphosphino)phenyl)-2,4-dihydro-1H-benzo[d][1,3]oxazine) showing a temp.-dependent equil. between a closed bidentate (LPN) and an opened tridentate (LPNO) form, has been synthesized and its coordination behavior toward ruthenium(II) centers studied. Under different exptl. conditions, two different species bearing the ligand in either its bidentate or tridentate coordination mode were isolated by reaction with Ru(PPh3)3Cl2. These species, resp. formulated as [Ru(PPh3)(LPNO)Cl2] (1) and [Ru(PPh3)(LPN)Cl2] (2), were fully characterized via NMR in soln. and by an x-ray structural detn. Notably, compd. 2 reacts with an excess of Et diazoacetate (EDA) in CH2Cl2 to give a stable ?3-diethyl maleate complex, [Ru(LPN)(cis-EtO(O)CCH:CHC(O)OEt)Cl2] (3). The crystal structure of 3 has also been detd. Substitution reactions with 4-picoline (4-Me-py) performed on 1 led to two new complexes: the neutral complex [Ru(4-Me-py)(LPNO)Cl2] (5) and the salt [Ru(4-Me-py)2(LPNO)Cl](Cl) (6a). The latter compd. catalyzed the intermol. cyclopropanation of styrene with EDA in high yields and with elevated cis diastereoselectivity (i.e., cis/trans = 80/20). [on SciFinder(R)]