Search results for "medicinal"
showing 10 items of 2966 documents
Synthesis, characterization and kinetics of the metallation of the intermediate compound to produce compound · (H2O) from Rh(II) tetraacetate
1998
Abstract Photochemical irradiation of mixtures of [Rh2(μ-O2CCH3)4]·(HOCH3)2 and P(2-(CH3O)C6H4)Ph2 (POMe) in CH2Cl2 solution (1:1 molar ratio) yields quantitatively compound [ Rh 2 (μ- O 2 CCH 3 ) 3 ( O 2 CCH 3 )(η 2 - P (2-( CH 3 O ) C 6 H 4 ) Ph 2 ]·( H 2 O ) (1) containing a POMe acting as a chelating equatorial ( P ) axial ( O ) donor ligand. This compound undergoes intramolecular CH activation reaction at one of the phenyl rings in CHCl3 or CH3COOH/toluene solution at room temperature to form the monometallated compound [ Rh 2 (μ- O 2 CCH 3 ) 3 (μ-( C C 3 H 4 ) P (2-( CH 3 O C 6 H 4 ) Ph )]· ( H 2 O ) ( 2 ). The kinetics of the 1 → bd2 reaction have been studied in acid media (CH3CO…
Mononuclear tungsten(VI) complexes with bis(phenolato) ligands: syntheses, characterisations and activity in ROMP reaction
2002
The reaction of bulky ligand precursor 2,2?-methylenebis(4-methyl-6-tert -butylphenol) (H2mbp) or 2,2?-ethylidenebis(4,6-di-tert butylphenol) (H2ebp) with trisdiolatotungsten(VI) complex [W(eg)3] 1 (eg � /ethanediolate dianion) provides heteroleptic complexes [W(mbp)(eg)2] 2 or [W(ebp)(eg)2] 3, respectively. Sterically less hindered 2,2?-dihydroxy-1,1?-dinaphtylmethane (H2dinap) forms heteroleptic disubstituted complex [W(dinap)2(eg)] 4. The X-ray crystal structure determinations confirmed that the isolated compounds are made of monomeric tris(diolato)tungsten(VI) molecules in which the central tungsten atom is bonded to six oxygen atoms forming a distorted octahedral coordination sphere ar…
(E)-2-{[1-(3,11-Dimethyl-4-methylene-10-oxo-1-phenyl-4,5,10,11-tetrahydro-1H-benzo[b]pyrazolo[3,4-f][1,5]diazocin-5-yl)ethylidene]amino}-N-methyl-N-(…
2013
The central eight-membered ring of the title compound, C40H36N8O2, deviates from the ideal boat conformation because the bond between the exo-ethylene group and the adjacent N atom is twisted by 60.0 (4)° due to steric hindrance. Its adjacent benzene and pyrazole rings are oriented almost perpendicular to each other, making a dihedral angle of 85.8 (3)°. In the crystal, the molecules are linked by C(ar)—H...O hydrogen bonds, generating a three-dimensional network.
Ligand Effects on the Chemoselectivity of Ortho-Metalated Rhodium(II) Catalyzed α-Diazo Ketone Transformations
1997
Rh2(OOCR)2(PC)2 complexes (PC = orthometalated phosphines, OOCR = carboxylates) with very polarizable ligands, such as aromatic rings directly joined to the rhodium atoms, control chemoselectivity in competitive metal carbene transformations of α-diazo ketones. These catalysts have a mixed set of ligands that allows choosing among a big selection of ligands to gradually affect the electronic and steric properties of the catalyst. Their selectivity depends on the electrophilicity of the ligands and the polarizability of the metalated aromatic rings. Thus, Rh2(OOCR)2(PC)2 compounds [PC = (C6H4)P(CH3)(C6H5), (p-CH3C6H3)P(p-CH3C6H4)2, (C6H4)P(C6H5)2; R = C3F7 or CF3] exhibit an exceptional sele…
Activation of the Cyano Group at Imidazole via Copper Stimulated Alcoholysis
2019
Reactions of 4,5-dicyano-1-methylimidazole with CuX2 (X = Cl, Br) in alcohol solvents (ethanol and methanol) resulted in the formation of Cu(II) carboximidate complexes [CuCl2(5- cyano-4-C(OEt)N-1-methylimidazole)(EtOH)] (1), [Cu2(µ
Unveiling the regioselectivity in electrophilic aromatic substitution reactions of deactivated benzenes through molecular electron density theory
2021
The origin of the meta regioselectivity in electrophilic aromatic substitution (EAS) reactions of deactivated benzene derivatives is herein analysed through Molecular Electron Density Theory (MEDT). To this end, the EAS reaction of benzenesulfonic acid with the nitronium NO2+ ion in H2SO4 solution has been studied at the ωB97X-D/6-311G(d,p) level. This reaction takes place through a two-step polar mechanism involving the formation of an unstable cation intermediate. The activation Gibbs free energies associated with the three competitive regioisomeric reaction paths are found in the narrow range of 15.5–18.3 kcal mol−1. By using the Eyring–Polanyi equation a relationship of 18.7 (ortho) : 8…
Ethylene oligomerization with 2-hydroxymethyl-5,6,7-trihydroquinolinyl-8-ylideneamine-Ni(II) chlorides
2021
Abstract A series of Ni complexes of the general formula [2-(MeOH)-8-{N(Ar)}C9H8N]NiCl2, where Ar = 2,6-Me2C6H3 in Ni1; 2,6-Et2C6H3 in Ni2; 2,6-i-Pr2C6H3 in Ni3; 2,4,6-Me3C6H2 in Ni4; 2,6-Et2-4-MeC6H2 in Ni5 and 2,4,6-t-Bu3C6H2 in Ni6 has been synthesized and characterized by elemental analysis and IR spectroscopy. On activation with MMAO or Et2AlCl, these complexes showed high activity in ethylene oligomerization, reaching 2.23 × 106 g·mol–1 (Ni) h–1 at 30 °C with the Al/Ni ratio of 5500 and 9.11 × 105 g·mol–1 (Ni) h–1 with the Al/Ni of 800, respectively. Moreover, the content of α-C4 indicated high selectivity exceeding 99% in the Ni/Et2AlCl system. Comparing with the previous report by o…
The oligomerisation of 3-hydroxy-1-alkynes with palladium(II) diketonates and phosphorus ligands as the catalytic system
1993
Abstract 3-Methylhex-1-yne-3-ol has been oligomerised by use of Pd(II) acetylacetonate with 31 different phosphorus ligands as catalyst, yielding a dimer (2,4-disubstituted but-1-en-3-yne) and a linear trimer (1,4,6-trisubstituted hexa-1,3-dien-5-yne) as the two main products. By input-output relations a variation of the diketonate and the P ligand, as weil as an alteration of the phosphorus/palladium ratio, has been connected with product ratios as dependent variables. Phosphines produced three association steps up to a cone angle of 170°; the third step representing a stop complex. For the first association the activity of the catalytic system and the portion of the 2,4-dimer increased wi…
An unprecedented, bridged dihydrogen complex of a cofacial metallodiporphyrin and its relevance to the bimolecular reductive elimination of hydrogen
1990
Recently, the authors characterized the first metalloporphyrin dihydrogen complex, Os(OEP)(H{sub 2}), and proposed that a similar ruthenium porphyrin dihydrogen complex, Ru(OEP)(H{sub 2}), is involved as an intermediate in the catalytic H/D isotopic exchange between water and hydrogen. They now report that treatment of a metal-metal-bonded cofacial ruthenium porphyrin dimer with a sterically bulky ligand in the presence of hydrogen gas has yielded the first known complex containing a dihydrogen ligand bound between two metals. Such a bridged dihydrogen complex is proposed as an intermediate in the bimolecular elimination of dihydrogen from two metalloporphyrin hydrides.
Kinetico-mechanistic studies of the acidolysis of Rh-C bonds in monocyclometallated dirhodium(II) acetato complexes; influence of electronic and ster…
2011
The protonation/demetallation reaction, in CD(3)COOD, of phosphine monometallated triacetato-bridged dirhodium(ii) complexes of general formulae [Rh(2)(μ-OOCCH(3))(3){(RC(5)CH(3))P(RC(6)H(4))(2)}(2)] has been studied from a kinetico-mechanistic perspective. The process has been monitored via the disappearance of the nuclear magnetic resonance signals of the protons present in the non-metallated ortho positions of the phosphine ligand and taking advantage of the relatively fast back metallation process that follows the acidolysis reaction, the sequence behaving as an overall equilibrium reaction. The process has a high associative character with important entropy demands, increasing both for…