RESUMEN

A series of new neutral mononuclear or dinuclear gold(I) complexes and a cyclic cationic tetranuclear amidogold(I) complex comprising of the phosphines 1,2-bis(dimethylphosphino)ethane (dmpe), µ-1,2-bis(diphenylphosphino)ethane (dppe), µ-1,3-bis(diphenylphosphino)propane (dppp), µ-1,5-bis(diphenylphosphino)pentane (dpppe), µ-1,6-bis(diphenylphosphino)hexane (dpph) or trimethylphosphine, and several N-heterocyclic ring systems (imidazolate, pyrazolate, 1,2,3-triazolate, 1,2,4-triazolate, pyrrolate, 9H-purine-9-ate or 9H-purine-6-amine-9-ate) as ligands, reveal intermolecular aurophilic interactions and 2D channels available for solvent molecules in some of their crystal structures. The antitumour activity of the acyclic gold(I) compounds is highly dependent on the substituents on the phosphorus atoms being highest for phenyl groups and lower for methyl groups. The activity of these compounds against selected cell lines is linked to the length of the carbon bridge between the two phosphorus atoms being highest with a bridge consisting of 5 or 6 carbons. Two compounds with the highest tumour specifities that contain dpppe and pyrazolate (a lipophilic compound) or 1,2,4-triazolate (a hydrophilic compound) induce an apoptotic cell death pathway and a maximum dose to Balb/C mice is tolerated.

Asunto(s)

Amidas/química , Oro/química , Compuestos Orgánicos de Oro/química , Fosfinas/química , Amidas/farmacología , Amidas/toxicidad , Animales , Antineoplásicos/farmacología , Apoptosis/efectos de los fármacos , División Celular/efectos de los fármacos , Línea Celular Tumoral , Supervivencia Celular/efectos de los fármacos , Células Cultivadas , Diarrea/inducido químicamente , Femenino , Células HeLa , Compuestos Heterocíclicos/química , Humanos , Células Jurkat , Potencial de la Membrana Mitocondrial/efectos de los fármacos , Ratones , Ratones Endogámicos BALB C , Modelos Moleculares , Estructura Molecular , Compuestos Orgánicos de Oro/farmacología , Compuestos Orgánicos de Oro/toxicidad , Pruebas de Toxicidad , Pérdida de Peso/efectos de los fármacos

RESUMEN

The title compound, [WCl(2)(C(9)H(10)N(2)S(2))(CO)(3)], is a hepta-coordinate tungsten(II) complex with a capped-octa-hedral coordination sphere in which one CO ligand caps a face formed by a chloro ligand and the two other carbonyls. The chloro ligands are mutually trans positioned at an angle of 156.98 (7)°. The chelating bis-(4-methyl-1,3-thia-zol-2-yl)methane ligand coordinates with the imine N atoms. In the crystal, mol-ecules are linked into chains parallel to [201] by weak C-H⋯O contacts between the CH(2) group of the bis-(4-methyl-thia-zol-2-yl)methane ligand and the O atom of the capping CO group.

RESUMEN

The title compound, C(30)H(16)N(4)O(4), reveals [Formula: see text] crystallographic and mol-ecular symmetry and accordingly the asymmetric unit comprises one half-mol-ecule. The dihedral angle between the planes of the two geminal benzoxazole rings is 74.39 (5)°. The packing features weak C-H⋯N and π-π inter-actions [centroid-centroid distance = 3.652 (1) Å].

RESUMEN

The acetonitrile ligand in the title compound, [W(CH(3)CN)(CO)(5)], is coordinated end-on to a penta-carbonyl-tungsten(0) fragment with a W-N bond length of 2.186 (4) Å, completing an octa-hedral coordination environment around the W atom.

RESUMEN

In the title compound, C(16)H(12)N(2)S(3), the two benzothia-zole groups are oriented differently with respect to the -CH(2)- groups, one being approximately staggered and one nearly eclipsed. A sulfur-π inter-action of 3.3627 (11) Šis observed between the bridging thio-ether S atom and a thia-zole ring. The crystal packing is further stabilized by inter-molecular C-H⋯N and C-H⋯π inter-actions.

RESUMEN

Ylideneamine functionalised heterocyclic ligands, 1,3-dimethyl-1,3-dihydro-benzimidazol-2-ylideneamine (I), 3-methyl-3H-benzothiazol-2-ylideneamine (II) or 3,4-dimethyl-3H-thiazol-2-ylideneamine (III), were employed in the preparation of a series of both charged and neutral gold(I) complexes consisting either of a Au(C(6)F(5)) fragment (1-3), a [Au(PPh(3))](+) unit (4-6) or a [Au(NHC)](+) unit (7) coordinated to the imine nitrogen of the neutral ylideneamine ligand. These complexes were fully characterised by various techniques including X-ray diffraction. In addition, the antitumour and antimalarial potential of selected compounds were assessed in a preliminary study aimed at determining the medicinal value of such compounds. Complexation of the azol-2-ylideneamine ligands with [Au(PPh(3))](+) increases their antitumour as well as antimalarial activity.

Asunto(s)

Antimaláricos/farmacología , Antineoplásicos/farmacología , Compuestos Organometálicos/farmacología , Plasmodium falciparum/efectos de los fármacos , Aminas/química , Antimaláricos/síntesis química , Antimaláricos/química , Antineoplásicos/síntesis química , Antineoplásicos/química , Proliferación Celular/efectos de los fármacos , Cristalografía por Rayos X , Relación Dosis-Respuesta a Droga , Ensayos de Selección de Medicamentos Antitumorales , Oro/química , Células HeLa , Compuestos Heterocíclicos/química , Humanos , Pruebas de Sensibilidad Microbiana , Modelos Moleculares , Estructura Molecular , Compuestos Organometálicos/síntesis química , Compuestos Organometálicos/química , Estereoisomerismo

RESUMEN

In the title compound, [Au(C(4)H(12)P(2)S(2))(2)](CF(3)SO(3)), the gold(I) atom is tightly bonded to two S atoms belonging to different ligand mol-ecules and forms two weaker contacts to the remaining S atoms. The coordination geometry around gold is inter-mediate between linear-dicoordinate and tetra-hedral with an S-Au-S angle of 161.49 (3)°.

RESUMEN

The asymmetric unit of the title solvate, C(30)H(16)N(4)S(4)·2CHCl(3), contains one half-molecule of tetrakis(2-benzothiazolyl)ethene, the complete molecule being generated by inversion symmetry, and one molecule of chloroform. Pairs of the benzothia-zole rings attached to the same carbon atom are almost perpendicular to each other, with an angle between planes of 85.74 (4)°. In the crystal, weak C-H⋯N and C-H⋯Cl interactions generate a three-dimensional network.

RESUMEN

We describe the formation of a complex [2]rotaxane both in solution and in the solid state. The rotaxane ring is composed of a cyclic trinuclear gold complex and the Au(PMe(3))(2)(+) rod is held in place by three aurophilic interactions to the ring Au atoms. The existence of the [2]rotaxane in solution is confirmed by VT-NMR and MS analysis.

RESUMEN

With the simplest of anionic Fischer-type carbene complexes acting as ligands, Cp(2)Zr(Cl){OCMe}M(CO)(5) compounds (M = Cr or W) promote alpha-olefin oligomerization and polymerization in the presence of MAO. Attaching an N-heterocyclic ring to the carbene carbon atom in similar precursors, allows a variety of hard metal ions and fragments to be captured by external bidentate coordination. The outcome of the attachment of a phosphorus or sulfur functionality to an alpha-carbon of an O-anionic carbene is formation of a bidentate ligand and then internal four-membered carbene-heteroatom chelate formation. alpha-Deprotonated carbene complexes are also precursors for remote, one-N, six-membered carbene complexes of various metals whereas alpha-C-, alpha-N- or alpha-O-deprotonated as well as beta-deprotonated Fischer-type carbene complexes display unique synthon properties towards Ph(3)PAu(+) and partake in unusual ensuing coordination of liberated group 6 metal carbonyl moieties to form dinuclear products.

RESUMEN

The title compound, [CrZr(C(5)H(5))(2)(C(2)H(3)O)Cl(CO)(5)], consists of two metal centres, with a (penta-carbonyl-chromium)oxymethyl-carbene group coordinating as a monodentate ligand to the zirconocene chloride. π-Delocalization through the Zr-O-C=Cr unit is indicated by a short Zr-O distance [2.041 (3) Å] and a nearly linear Zr-O-C angle [170.5 (3)°]. Mol-ecules are aligned with their mol-ecular planes (through Zr, Cl, carbene and Cr) parallel to the ab plane. C-H⋯Cl inter-actions result in zigzag chains of mol-ecules propagating parallel to the b axis.

RESUMEN

In the crystal structure of the title ionic compound (C(7)H(6)NS)[AuCl(4)]·C(4)H(8)O, the [AuCl(4)](-) anion shows a typical square-planar geometry. Numerous weak C-H⋯Cl hydrogen bonds between [AuCl(4)](-) and the 1,3-benzothia-zolium units form layers comprised of 24-membered rings in which hydrogen-bonded tetra-hydro-furan (THF) solvent mol-ecules are accommodated. C-H⋯Cl inter-actions between THF and [AuCl(4)](-) from adjacent layers result in bilayers. These are further stabilized by π-π inter-actions between the thia-zole and benzene rings [centroid-centroid distance = 3.971 (3) Å], resulting in the formation of a three-dimensional supra-molecular assembly.

RESUMEN

In the title compound, [Ag(C(7)H(6)N(2)S)(2)]NO(3)·C(3)H(6)O, the Ag(I) ion is coordinated to two benzothia-zol-2-amine ligands via the thia-zole N atoms in an approximately linear arrangement. The dihedral angle between the mean planes of the two 1,3-benzothia-zole groups is 5.9 (3)°. Both amine groups on the ligands are oriented in the same direction and are engaged in N-H⋯O hydrogen bonding with the nitrate counter-anion, forming one-dimensional columns along the b-axis direction. Voids created by inefficient crystal packing are occupied by acetone solvent mol-ecules which are disordered over two sites with occupancies of 0.563 (11) and 0.437 (11).

RESUMEN

The title compound, [Au(2)(C(26)H(24)P(2))(2)](CF(3)SO(3))(2)·2CH(3)CN, comprises a cyclic cation with a short intra-molecular aurophilic inter-action of 2.9220 (3) Å. The trifluoro-methane-sulfonate anions and acetonitrile solvent mol-ecules are located in channels formed by the complex cations that run along the crystallographic c axis. Each counter-anion is also engaged in a C-H⋯O contact with one of the methyl-ene H atoms of a 1,2-bis-(diphenyl-phosphino)ethane (dppe) ligand; another C-H⋯O contact involving an aromatic H atom is also observed.

RESUMEN

The metal atom in the title ylid-gold(I) adduct, [Au(C(6)F(5))(C(26)H(23)P)]·C(4)H(10)O, exists in a linear coordination environment [C-Au-C = 174.1 (2)°]. The mol-ecule has a short intra-molecular contact involving an aromatic H atom (Au⋯H = 2.64 Å); two adjacent mol-ecules are linked by an Au⋯H(ylid) inter-action (Au⋯H = 3.14 Å).

RESUMEN

The title compound, (C(44)H(38)P(2))[AuCl(C(6)F(5))](2)·2CH(2)Cl(2), crystallizes with a twofold rotation axis through the central benzene ring in the bis-phospho-nium dication. In the crystal, the dications and anions are ordered into columns running parallel to the c axis by contacts of the pro-ylidic CH(2) groups with the Cl atom of one and an ortho-F atom of another anion. The space between the columns is occupied by CH(2)Cl(2) solvent mol-ecules.

RESUMEN

New preparative methods for gold carbene complexes have been developed and older ones modified to prepare compounds with specific inherent properties for targeted applications. One of the important areas of application that has grown rapidly and wherein carbene complexes are increasingly significant falls within the field of medicine. Sophisticated theoretical calculations have accompanied many synthetic studies. These aspects are covered in this critical review (65 references).

Asunto(s)

Oro/química , Metano/análogos & derivados , Animales , Catálisis , Gases , Oro/uso terapéutico , Humanos , Metano/síntesis química , Metano/química , Metano/uso terapéutico

RESUMEN

A whole library of six-membered N-heterocyclic carbene complexes of Ni(ii) and Pd(ii) were prepared by oxidative substitution. In some of these compounds the heteroatom occurs in a position distant from the carbene donor atom. Combined structural and physical data, especially (13)C NMR results, indicate carbene character in such ligands. DFT quantum mechanical calculation at the RI-BP56/SVP level allowed the extraction of valuable chemical information predicting that rNHC (r = remote) ligands would bond more strongly than their nNHC (n = normal) isomers. This result is also corroborated by calculations on the metal complexes themselves. Orbital overlap (mainly sigma) follows the order N(2)HC(5) < nN(1)HC(6) < rN(1)HC(6) when ligands derived from halo-imidazolium and halo-pyridinium salts are compared. In C-C coupling catalysis using Pd(ii) and Ni(ii) complexes, the simple one-N, six-membered carbene complexes are superior to simple two-N, five-membered examples but clear differentiation between nNHC and rNHC precatalysts in the former family, is not always possible.

RESUMEN

The title compound, [ZrW(C(5)H(5))(2)(C(2)H(3)O)Cl(CO)(5)] or [W(CO)(5)C(CH(3))OZr(C(5)H(5))(2)Cl], consists of two metal centres, with a (tungsten penta-carbon-yl)oxymethyl-carbene group coordinating as a monodentate ligand to the chloridozirconocene. The two halves of the mol-ecule are related by a crystallographic mirror plane. Delocalization through the Zr-O-C=W unit is indicated by a short Zr-O distance and a nearly linear Zr-O-C angle.

RESUMEN

The title compound, [HfW(C(5)H(5))(2)(C(7)H(5)O)Cl(CO)(5)] or [W(CO)(5)(C(7)H(5)O){Hf(C(5)H(5))(2)Cl}], contains two metal centres, with a (tungstenpenta-carbon-yl)oxy-phenyl-carbene unit coordinated to a hafnocene chloride. The Hf-O-C angle is nearly linear, and the C=O distance is slightly shorter than for equivalent alkoxy-carbenes. One of the cyclo-penta-dienyl (Cp) rings undergoes an offset face-to-face π-π inter-action [3.495 (7) Å] with the symmetry-related Cp ring of a neighbouring mol-ecule.