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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
    Ni(II) and Pd(II) pyridinyloxazolidine-compounds: synthesis, X-ray characterisation and catalytic activities in the aza-Michael reaction
    (2012)
    Ardizzoia, G. Attilio
    ;
    Brenna, Stefano
    ;
    Therrien, Bruno 
    The 3-phenyl-2-(pyridin-2-yl)oxazolidine ligand (ppo) was synthesized and its coordination behavior regarding Ni(II) and Pd(II) centers was studied. The reaction with K2PdCl4 affords [Pd(N,N'-ppo)Cl2] (1), in which ppo chelates to Pd via the pyridyl-nitrogen and the oxazolyl nitrogen atoms. The reaction of ppo with NiCl2·6H2O produces [Ni(N,O-ppo)2Cl2] (2), in which two ppo ligands are coordinated via the pyridyl-nitrogen and the oxygen atom of the oxazolidine ring. The x-ray diffraction anal. of the complexes confirms a square planar geometry for Pd(II) in 1 and an octahedral configuration around Ni(II) in 2, which, to the best of the authors' knowledge, represents the first reported example of a structurally characterized nickel-oxazolidine compd. Both complexes prove to be active catalysts under mild conditions in the aza-Michael reaction of (E)-4-phenylbut-3-en-2-one (benzalacetone) with aliph. amines. [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)]
  • Publication
    Accès libre
    The Adaptable Coordination Chemistry of 6-Chloro-2-(quinolin-2-yl)-2,4-dihydro-1H-benzo[d][1,3]oxazine Towards Zinc(II) and Mercury(II)
    (2010)
    Attilio Ardizzoia, G.
    ;
    Brenna, Stefano
    ;
    Therrien, Bruno 
    The coordination chemistry of 6-chloro-2-(quinolin-2-yl)-2,4-dihydro-1H-benzo[d][1,3]oxazine (LH2) towards zinc and mercury has been explored. The ligand exhibits high versatility and provides different environments to the metal centre as a function of its diverse coordination modes. In one of the isolated and characterized complexes, [Zn(LOH)Cl2], the zinc centre is found pentacoordinated with the ligand present in an iminic “open” structure. The oxidized form, which contains the 4H-benzo[d][1,3]oxazine part (L), is also encountered in [Zn(L)Cl2], whereas the crystal structure of the trinuclear compound [Hg3(LH2)2Cl6] shows the ligand LH2 in its original arrangement.