Abdelhamid Mousser

Complexation d'iminopyridines par le sel de zeise: voie d'access a des conjugues estradiol-cis-dichloro platine. Etude structure du complexe cis-PtCl2[C5H4NCH2NC(CH3)C6H4OH],H2O

Abstract In order to synthesize penta- and hexa-gonal platinum(II) metallocycles, bidentate ligands such as iminopyridines (L) have been prepared and characterized. The (2-pyridyl)CHNR 1 and (2-pyridyl)CH 2 NCR 1 R 2 ligands react with Zeises salt to afford directly the pentagonal chelates PtCl 2 L. Their structure and the cis -stereo-chemistry were shown by the usual spectroscopic methods and for cis -PtCl 2 [C 5 H 4 NCH 2 NC(CH 3 )C 6 H 4 OH],H 2 O by an X-ray diffraction study. On the other hand, the (2-pyridyl)(CH 2 ) 2 NCR 1 R 2 ligands do not afford the expected hexagonal metallocycles; instead, after complexation at the nitrogen atom of the imine they give rise to the (2-pyridyl)ethylamine complex formed after hydrolysis of the coordinated ligands. Complexes trans -[ethylene][(2-pyridyl)(CH 2 ) 2 NCR 1 R 2 ]PtCl 2 represent when R 1 is estradiol a model for “cytotoxic with delayed activity”.

Complexes binucleaires de fer carbonyle liaison σ-metal-carbone: Synthese, etude structurale et proprietes

Abstract Dithioesters R1C(S)SR2 react with [Fe2(CO)9] to afford binuclear complexes (Co)3FeC(R1)S(R2)SFe(CO)3 (I) in which the organic ligand gives six electrons to the Fe2(CO)6 skeleton. Spectroscopic data show the existence of carboniron σ bond with creation of a chiral center. This is confirmed by single-crystal X-ray structure determination of complex Ig(R1 = C4H3S, R2 = Me). This structure shows that coordination imposes important geometrical constraints. 13C NMR studies reveal a temperature dependant dynamic behaviour for complexes I in solution. The carbonyl fluxionality occurs around each metal atom independently. Electrophilic substitution of the coordinated organic ligand may occur despite the complex fragility in a basic medium or in the presence of oxidizing agents.

Substitutions selectives de carbonyles dans les complexes polynucleaires: VI.Structures et proprietes des complexes dithioester-Fe2(CO)5L☆

Abstract The binuclear complexes [R 1 (C(S)SR 2 ]Fe 2 (CO) 5 L (L= CO) obtained by complexation of dithioesters, react under thermal activation with ligands such as L = P(OMe) 3 , CNR, PHPh 2 to afford exclusively monosubstituted products. A single crystal X-ray structure determination of the complex, [PhC(S)-SMe]Fe 2 (CO) 5 P(OMe) 3 shows the regiospecificity of monosubstitution at the metal atom not bonded to the functional carbon atom. 13 C and 31 P studies show interesting dynamic behaviour for the complexes with L = P(OMe) 3 .

Iron atom discrimination by carbon during the fragmentation of a ligand around a FeFe bond. Crystal structure [μ-η3-RCH2OC(S)SMeFe2(CO)5P(OMe)3]

Abstract The substituted compound [μ-η 3 RCH 2 OC(S)SMeFe 2 (CO) 5 P(OMe) 3 ] ( 3 ) (the structure of which was determined by X-ray diffraction), undergoes a ligand fragmentation leading to the known substituted compound [μ-η 2 (RCH 2 OCS)Fe 2 - (CO) 5 P(OMe) 3 μ-SMe] ( 4 ). Evidently during the rearrangement the carbon atom of the bridging ligand migrates from one iron atom to the adjacent iron that bears the phosphite ligand.

1-[4-({4-[(E)-(2-Hy­droxy­naphthalen-1-yl)methyl­idene­amino]­phen­yl}sulfan­yl)phen­yl]ethanone

The title Schiff base compound, C25H19NO2S, crystallizes in a statistically disordered structure comprising keto and enol tautomeric forms. In the enol form, the benzenoid arrangment is promoted by a strong intramolecular O—H⋯N hydrogen bond and adopts an E conformation about the imine bond. In the keto form there is an intramolecular N—H⋯O hydrogen bond. In the crystal, an extended network of C—H⋯O hydrogen bonds stabilizes columns parallel to the c axis, forming large voids (there are four cavities of 108 Å3 per unit cell) with highly disordered residual electron density. The SQUEEZE procedure in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148–155] was used to eliminate the contribution of this electron density from the intensity data, and the solvent-free model was employed for the final refinement. The contribution of this undetermined solvent was ignored in the calculation of the unit-cell characteristics.

Penta­carbon­yl(imidazolidine-2-thione-κS)tungsten(0)

In the title complex, [W(C3H6N2S)(CO)5], the W atom displays an octahedral coordination with five CO molecules and an imidazolidine-2-thione molecule. The W(CO)5 unit is coordinated by the cyclic thione ligand through a W—S dative bond. The W—S and C—S bond lengths are 2.599 (2) and 1.711 (9) Å, respectively. This last distance is significantly longer than that of free cyclic thioureas. The geometry of the title compound suggests sp 3-hybridization of the S atom caused by the greatly polarized linkage W—S—C bond angle, which is close to tetrahedral [109.50 (3)°]. In the crystal packing, N—H⋯O and N—H⋯S hydrogen-bonding interactions stabilize the structure and build up chains parallel to [101].

Dimeric (2-cyano-phenolato-κO){2,2'-[ethyl-enebis(nitrilo-methyl-idyne)]diphenolato-κO,N,N',O'}manganese(III) monohydrate.

The molecules of the title compound, [Mn(C7H4NO)(C16H14N2O2)]·H2O, form dimers in the solid state across a crystallographic inversion center. The bridging Mn2O2 group is built of phenoxy groups, and is asymmetric, with an Mn—O distances of 1.9002 (13) and 2.6236 (14) Å. A substantial cavity between the two Mn atoms [Mn⋯Mn = 3.5082 (4) Å] is produced by the formation of the dimer. In the crystal, an extended network of O—H⋯O hydrogen-bonding interactions stabilizes the structure.

Carbon-ligand migration during the electron-transfer catalyzed stepwise replacement of two carbon monoxide ligands in a doubly-bridge di-iron compound

Abstract The complexes [(μ-η 2 -ROC(1)S)Fe 2 (CO) 6 (μ-SMe)] ( 1 ), undergo selective replacement of one CO by P(OMe) 3 (L 1 ) or t-BuNC (L 2 ) to give the monosubstituted compounds 2 and 3 , respectively when L 1 or L 2 is bonded to Fe(1) bearing the carbene ligand C(1). When a second CO ligand is displaced from 2 or 3 by electron-transfer catalysis both give a complex ( 6 ) in which L 2 and L 1 are linked to Fe(1) and Fe(2), respectively; moreover L 1 in 2 and L 2 in 3 are displaced by the ligand present in the solution to give bis-isonitriles and bis-phosphites. The structure of 6 has been determined by X-ray diffraction and the results are discussed in terms of the assumption that the ligand exchange occurs in an intermediate in which C(1) becomes bonded to both metal atoms and consequently can rotate about the Fe-Fe axis.

Crystal structure of (E)-1-[4-({4-[(4-meth-oxy-benzyl-idene)amino]-phen-yl}sulfan-yl)phen-yl]ethan-1-one.

The title Schiff base compound, C22H19NO2S, crystallized with two independent molecules (A and B) in the asymmetric unit. Both molecules have an E conformation about the C=N bond. The two molecules differ in the orientation of the aromatic rings with respect to each other. The outer 4-methoxybenzene ring is inclined to the central benzene ring and the outer 4-acetylbenzene ring by 1.80 (19) and 63.73 (19)°, respectively, in molecule A, and by 6.72 (18) and 68.53 (19)°, respectively, in molecule B. The two outer benzene rings are inclined to one another by 63.77 (18) and 63.19 (18)° in molecules A and B, respectively. In the crystal, the individual molecules stack in columns along [010], and are linked by a number of C—H⋯π interactions, forming slabs lying parallel to (001).

(Benzene­carbothio­amide-κS)­penta­carbonyl­tungsten(0)

The asymmetric unit of the title complex, [W(C7H7NS)(CO)5], comprises two independent molecules. In each, the W atom is coordinated by five CO groups and the S atom of the benzencarbothioamide ligand in a distorted octahedral geometry. The crystal packing can be described as undulating layers of W(CO)5 and benzenecarbothioamide parallel to (001). In the crystal, components are linked via intermolecular N—H⋯O and C—H⋯O hydrogen bonds to form a dimeric chains along the [010] direction. Intramolecular N—H⋯C interactions are also observed.