0000000001303123
AUTHOR
Yves Le Mest
Unprecedented reactivity of a Schiff base ligand in the co-ordination sphere of copper(I) complex towards β-diketones. Synthesis and X-ray characterisation of a new copper(I) complex
International audience; The reactions of the copper(I) derivative [CuL(THF)(CH3CN)]PF6 (1), in which L is the di-imine/pyridine ligand 2,6-bis[1-(2,6-diisopropylphenylimino)ethyl]pyridine, with different β-diketones (2,4-pentanedione (acacH), 1,3-diphenyl-1,3-propanedione (dbm)) yielded the new Cu(I) salt [CuL′2]PF6 (2) (L′: 2-[acetyl]-6-[1-(2,6-diisopropylphenylimino)ethyl]pyridine). These reactions of β-diketones with a di-imine/pyridine ligand co-ordinated to a Cu(I) centre constitute the first example of a partial hydrolysis of such a Schiff base within the inner sphere of a Cu centre. Compound 2·acaH has been characterised by X-ray crystallography. © 2002 Elsevier Science B.V. All righ…
Quadruply-bonded dimolybdenum compounds: Reactivity towards TCNE. Structural evidences for the 1-D polymer [Mo2(O2 CCF3)4(TCNE)]∞
cited By 3; International audience; Reaction of [Mo2(O2CR)4] (R = CF 3, 1) with TCNE in toluene affords the new compound [Mo2(O2CCF3)4 (TCNE)·6H5CH3 (2). The structure of 2 is built on [Mo2(O2 CCF3)4] fragments having the usual paddlewheel structure of 1 (Mo-Mo 2.1117(8) Å) and TCNE units. Each polynitrile moiety acts as a bridging ligand between two Mo2 fragments (Mo-N 2.875(4) Å) affording 1-D polymeric chains crossing in the crystal; the toluene molecules occupy the cavities between the chains. 13C NMR, IR and electrochemical data clearly show that formation of 2 does not involve electron density transfer from dimolybdenum fragment to the TCNE unit, which remains in 2 in its neutral stat…
Aza and cyanobridged tripodal dinuclear copper(II) complexes: Electrochemical studies and structural evidence for an original azacyanocarbanion
International audience; The reactivity of the mononuclear [Cu(TMPA)(L)] n+ complex (TMPA: tris(2-methylpyridine) amine, L: CH3CN, H2O) towards two different bridging species (tetracyanoethylene, 4,40-bipyridine) was investigated. The dinuclear complex [(mu-4,40-bipy)Cu-II(TMPA)(2)](CF3SO3)(4) (1) was synthesised and analysed by Xray diffraction (XRD). Magnetic studies revealed that this derivative displays very weak antiferromagnetic interactions between the two metal centres (2J = -0.69 cm(-1)). Solution studies (EPR spectroscopy and voltammetry) evidenced the lability of the bridged neutral bipyridine ligand in acetonitrile. The reaction of TCNE (TCNE: tetracyanoethylene) with the copper(…
Pentacyanopropenide group as ligand in organometallic chemistry. Crystal structure and electrochemical studies of (Et4N)[W(CO)5{(C(CN)2C(CN)C(CN)2}]
Abstract The title complex has been obtained by reaction of the tetraethylammonium pentacyanopropenide with tungsten hexacarbonyl in acetone. Its crystal structure involves discrete [W(CO)5{C3(CN)5}]− anions in which the organic fragment is N-coordinated via one of the nitrogen atoms of a cyano group borne by one of the terminal carbon atoms of the allylic skeleton. The anion presents a distorted octahedral coordination with a W–N bond length [2.168(5) A] considerably longer than the W–C bond lengths [cis-W–C in the range 1.998(7)–2.068(4) A; trans-W–C 1.962(7) A]. Cyclic voltammograms of this complex, recorded in CH2Cl2 and CH3CN (Bu4NPF6 0.1 M), display a quasi-reversible reduction and ir…
Unexpected behaviour of copper(I) towards a tridentate Schiff base: Synthesis, structure and properties of new Cu(I)-Cu(II) and Cu(II) complexes
cited By 17; International audience; The reaction of CuBr with 2,6-bis[1-(2,6-diisopropylphenylimino)ethyl]pyridine L afforded a new Cu(I)-Cu(II) derivative [CuBrL]2[Cu2Br4] (1), while the reaction of [Cu(CH3CN)4]PF6 with L in THF yielded the new Cu(I) compound CuL(THF)(CH3CN)PF6 (2). Derivative 2 further reacted with halogenated solvents to yield halogeno-Cu(II) salts, [CuClL]PF6 (3) using CHCl3 and [CuBrL]Br3 (4) using CHBr3. Compounds 1, 3 and 4 have been fully characterised by X-ray crystallography; they contain essentially similar [CuXL]+ cations with a square planar copper(II) co-ordination. However, the structure of compound 1 must be viewed as built of tetranuclear units since two […
“Two-Story” Calix[6]arene-Based Zinc and Copper Complexes: Structure, Properties, and O 2 Binding
International audience; A new “two-story” calix[6]arene-based ligand was synthesized, and its coordination chemistry was explored. It presents a tren cap connected to the calixarene small rim through three amido spacers. X-ray diffraction studies of its metal complexes revealed a six-coordinate ZnII complex with all of the carbonyl groups of the amido arms bound and a five-coordinate CuII complex with only one amido arm bound. These dicationic complexes were poorly responsive toward exogenous neutral donors, but the amido arms were readily displaced by small anions or deprotonated with a base to give the corresponding monocationic complexes. Cyclic voltammetry in various solvents showed a r…
CCDC 959981: Experimental Crystal Structure Determination
Related Article: Antoine Gomila, Benedicte Douziech, Nathalie Cosquer, Nicolas Le Poul, Francois Michaud, Carlos J. Gomez-Garcia, Yves Le Mest, Francoise Conan|2014|Inorg.Chim.Acta|411|67|doi:10.1016/j.ica.2013.11.024
CCDC 959979: Experimental Crystal Structure Determination
Related Article: Antoine Gomila, Benedicte Douziech, Nathalie Cosquer, Nicolas Le Poul, Francois Michaud, Carlos J. Gomez-Garcia, Yves Le Mest, Francoise Conan|2014|Inorg.Chim.Acta|411|67|doi:10.1016/j.ica.2013.11.024
CCDC 1541407: Experimental Crystal Structure Determination
Related Article: Gaël De Leener, Diana Over, Coryse Smet, Damien Cornut, Ana Gabriela Porras-Gutierrez, Isidoro López, Bénédicte Douziech, Nicolas Le Poul, Filip Topić, Kari Rissanen, Yves Le Mest, Ivan Jabin, and Olivia Reinaud|2017|Inorg.Chem.|56|10971|doi:10.1021/acs.inorgchem.7b01225
CCDC 1541408: Experimental Crystal Structure Determination
Related Article: Gaël De Leener, Diana Over, Coryse Smet, Damien Cornut, Ana Gabriela Porras-Gutierrez, Isidoro López, Bénédicte Douziech, Nicolas Le Poul, Filip Topić, Kari Rissanen, Yves Le Mest, Ivan Jabin, and Olivia Reinaud|2017|Inorg.Chem.|56|10971|doi:10.1021/acs.inorgchem.7b01225
CCDC 959980: Experimental Crystal Structure Determination
Related Article: Antoine Gomila, Benedicte Douziech, Nathalie Cosquer, Nicolas Le Poul, Francois Michaud, Carlos J. Gomez-Garcia, Yves Le Mest, Francoise Conan|2014|Inorg.Chim.Acta|411|67|doi:10.1016/j.ica.2013.11.024