0000000000056502
AUTHOR
Jean Sala Pala
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…
Heptanuclear hydroxo-bridged copper cluster of the dicubane-like type: structural and magnetic characterisations of [Cu7(OH)6Cl2(pn)6(H2O)2](C(CN)3)4Cl2 (pn = 1,3-diaminopropane)
A new polynuclear copper(II) complex [Cu7(OH)6Cl2- (pn)6(H2O)2](C(CN)3)4Cl2 with hydroxo-bridging ligands has been prepared; the centrosymmetric cluster cation can be described as two Cu4O3Cl distorted cubane units sharing one copper cation. Clemente Juan, Juan Modesto, Juan.M.Clemente@uv.es ; Gomez Garcia, Carlos Jose, Carlos.Gomez@uv.es ; Coronado Miralles, Eugenio, Eugenio.Coronado@uv.es
New coordination polymers with a 2,2-dicyano-1-ethoxyethenolate (dcne–) bridging ligand: syntheses, structural characterisation and magnetic properties of [M(dcne)2(H2O)2] (M = MnII, FeII, CoII, NiII and ZnII) and [Cu(dcne)2(H2O)]
New polymeric materials [M(dcne)2(H2O)2] with M = MnII (1), FeII (2), CoII (3), NiII (4) and ZnII (5) and [Cu(dcne)2(H2O)] (6) (dcne− = [(CN)2CC(O)OEt)]− = 2,2-dicyano-1-ethoxyethenolate anion) have been synthesised and characterised by infrared spectroscopy, X-ray crystallography and magnetic measurements. In these compounds, each organic ligand acts in a bridging mode with its two nitrogen atoms bound to two different metal cations. In compounds 1–5, each metal cation has a pseudo-octahedral cis-MN4O2 environment with four nitrogen atoms from four different organic ligands and two oxygen atoms from two water molecules. In compound 6, only one water molecule is coordinated and each 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…
Discrete Dinuclear Complexes and Two‐Dimensional Architectures from Bridging Polynitrile and Bipyrimidine (bpym) Ligands: Syntheses, Structures and Magnetic Properties of [M 2 (bpym)(dcne) 4 (H 2 O) 2 ] (M = Mn II , Co II ) and [M 2 (bpym)(dcne) 4 (H 2 O) 4 ]·2H 2 O (M = Fe II , Cu II ) (dcne − = [(CN) 2 CC(O)OEt)] − )
One-pot reactions in aqueous solutions of the polynitrile anion dcne− {2,2-dicyano-1-ethoxyethenolate = [(CN)2CC(O)OEt)]−] with the MII ions (M = Mn, Fe, Co, Cu) in the presence of bpym (2,2′-bipyrimidine) afford the first mixed dcne/bpym compounds [M2(bpym)(dcne)4(H2O)2] (1: M = Mn; 2: M = Co) and [M2(bpym)(dcne)4(H2O)4]·2H2O (3: M = Fe; 4: M = Cu). The new compounds have been characterized by IR spectroscopy and X-ray crystallography. Compounds 1 and 2 are isostructural, with each metal ion being located in an MN5O pseudo-octahedral environment with three N atoms coming from three dcne− ligands, two nitrogen atoms from bpym and one oxygen atom from a water molecule. The extended structure…
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 […
[Cu(tn)]3[Cr(CN)6]2·3H2O: A unique two-dimensional Cu-Cr cyano-bridged ferromagnet (tn = 1,3-diaminopropane)
Reaction of the two-coordinate ‘assembling complex-ligand’ [Cu(tn)]2+ with the building block [Cr(CN)6]32 leads to a unique two-dimensional Cu–Cr cyano-bridged ferromagnet with unusual m3- and m4-bridging [Cu(tn)]2+ units. Gomez Garcia, Carlos Jose, Carlos.Gomez@uv.es
New charge transfer salts of two organic π-donors of the tetrathiafulvalene type with the paramagnetic [Cr(NCS)6]3- anion
cited By 9; International audience; The electrochemical combination of the paramagnetic anion [Cr(NCS)6]3- with the organic π-donors bis(ethylenedithio)tetrathiafulvalene (ET) and 4,5-bis(2-hydroxyethylthio) -4′,5′-ethylenedithiotetrathiafulvalene (DHET-EDTTTF) leads to two new radical cation salts, namely (ET)4 [Cr(NCS 6]·PhCN 1 and (DHET-EDTTTF)2 (NEt4)[Cr(NCS)6] 2. Both have been characterized by X-ray crystallography, magnetic and resistivity measurements. The structure of 1 consists of alternating inorganic layers generated by the anions and organic layers in which the PhCN molecules are inserted; the organic sub-lattice is built up from four different ET units, three of them with a ch…