A5085152040- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Metalloenzymes and iron-sulfur proteins
- Inorganic Chemistry and Materials
- Organometallic Complex Synthesis and Catalysis
- Nanocluster Synthesis and Applications
- Organic Chemistry Cycloaddition Reactions
- Catalytic Alkyne Reactions
- 2D Materials and Applications
- Organometallic Compounds Synthesis and Characterization
- Analytical Chemistry and Sensors
- Polyoxometalates: Synthesis and Applications
- Inorganic Fluorides and Related Compounds
- Metal complexes synthesis and properties
- Electrochemical sensors and biosensors
- Crystallography and molecular interactions
- Water Quality Monitoring and Analysis
- Photochemistry and Electron Transfer Studies
- Machine Learning in Materials Science
- Free Radicals and Antioxidants
- Corrosion Behavior and Inhibition
- Synthetic Organic Chemistry Methods
- Chemistry and Stereochemistry Studies
Universidad de Cádiz
2009-2021
Hospital Universitario Puerto Real
2016
University of Debrecen
2016
An alternative reactivity mode of electron-rich allenylidene complexes via alkenylcarbyne species is reported for the first time in ruthenium bearing monodentate phosphine ligands (triethylphosphine). Allenylidene have been prepared and characterized from [Cp*RuCl(PEt3)2] a series propargyl alcohols different substituents (HC≡CCRR′(OH), where R, R′ = Ph, Ph; R H, p-MeO-C6H4, C6H5, p-F-C6H4). Alkenylcarbyne are by protonation precursors. The X-ray structures one secondary (R, Ph) complex...
The [Mo3S4Cl3(dhprpe)3]+ (1+) cluster cation has been prepared by reaction between Mo3S4Cl4(PPh3)3 (solvent)2 and the water-soluble 1,2-bis(bis(hydroxypropyl)phosphino)ethane (dhprpe, L) ligand. crystal structure of [1]2[Mo6Cl14] determined X-ray diffraction methods shows typical incomplete cuboidal with a capping three bridging sulfides. octahedral coordination around each metal center is completed chlorine two phosphorus atoms diphosphine Depending on pH, hydroxo group functionalized can...
Water-soluble [M3S4X3(dhbupe)3](+) diphosphino complexes (dhbupe = 1,2-bis(bis(hydroxybutyl)phosphino)ethane), 1(+) (M Mo, X Cl) and 2(+) W; Br), have been synthesized by extending the procedure used for preparation of their hydroxypropyl analogues reaction M3S4(PPh3)3X4(solvent)x molecular clusters with corresponding 1,2-bis(bishydroxyalkyl)diphosphine. The solid state structure cation possesses a C3 symmetry cuboidal M3S4 unit, outer positions are occupied one halogen two phosphorus atoms...
The aminophosphine ligand (2-aminoethyl)diphenylphosphine (edpp) has been coordinated to the W3(μ-S)(μ-S)3 cluster unit afford trimetallic complex [W3S4Br3(edpp)3]+ (1+) in a one-step synthesis process with high yields. Related [W3S4X3(edpp)3]+ clusters (X = F–, Cl–, NCS–; 2+–4+) have isolated by treating 1+ corresponding halide or pseudohalide salt. structure of complexes 4+ contains an incomplete W3S4 cubane-type unit, and only one possible isomers is formed: phosphorus atoms trans capping...
Treatment of the triangular [Mo3S4Cl3(dbbpy)3]Cl cluster ([1]Cl) with CuCl produces a novel tetrametallic cuboidal [Mo3(CuCl)S4Cl3(dbbpy)3][CuCl2] ([2][CuCl2]), whose crystal structure was determined by X-ray diffraction (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). This species, which contains two distinct types Cu(I), is first example diimine-functionalized heterometallic M3M'S4 cluster. Kinetics studies on both formation cubane from parent trinuclear and its dissociation after treatment...
Newly synthesised molibdenum diimino clusters interact with alkynes leading to dithiolene species.
We report a trinuclear Mo3S4 diamino cluster that promotes the semihydrogenation of alkynes. Based on experimental and computational results, we propose an unprecedented mechanism in which only three bridging sulfurs act as active site for this transformation. In first step, two these μ-S ligands react with alkyne to form dithiolene adduct; process is formally analogous olefin adsorption MoS2 surfaces. Then, H2 activation occurs way involves third center, cooperation one carbon atoms....
Abstract A study, involving kinetic measurements on the stopped‐flow and conventional UV/Vis timescales, ESI‐MS, NMR spectroscopy DFT calculations, has been carried out to understand mechanism of reaction [Mo 3 S 4 (acac) (py) ][PF 6 ] ([ 1 ]PF ; acac=acetylacetonate, py=pyridine) with two RCCR alkynes (R=CH 2 OH (btd), COOH (adc)) in CH CN. Both reactions show polyphasic kinetics, but experimental computational data indicate that alkyne activation occurs a single step through concerted...
The synthesis, crystal structure and solution characterization of the cubane-type [Mo3(FeCl)S4(dmpe)3Cl3] (1) (dmpe = 1,2-bis(dimethylphophane-ethane)) cluster are reported ligand substitution processes chloride by thiophenolate investigated. kinetics intimate mechanism these substitutions reveal that compound 1 undergoes a number Fe Mo site specific reactions in acetonitrile solutions. In particular, PhS− coordination at tetrahedral proceeds single resolved kinetic step whereas such sites...
Reaction of [Mo3(μ3-S)(μ-S)3] clusters with alkynes usually leads to formation two C–S bonds between the alkyne and bridging sulfides. The resulting compounds contain a alkenedithiolate ligand, metal centers appear play passive role despite reactions at those sites being well illustrated for this kind cluster. A detailed study including kinetic measurements DFT calculations has been carried out understand mechanism reaction [Mo3(μ3-S)(μ-S)3(H2O)9]4+ (1) cluster different alkynes,...
Abstract Here, the kinetics of concerted [3 + 2] cycloaddition reaction between [Mo 3 (μ ‐S)(μ‐S) Cl (dmen) ] (dmen = N,N ′‐dimethyl‐ethylenediamine) ([ 1 ) cluster and various alkynes to form dithiolene derivatives is thoroughly studied, with measurements at different temperatures pressures allowing determination free energies volumes activation. These parameters, together available single‐crystal X‐ray diffraction structures, are used test a number commonly density functional theory (DFT)...
Detailed studies through stopped‐flow 31 P{ 1 H} NMR spectroscopy and ESI‐MS were performed for the reactions of [W 3 S 4 Br (edpp) ] + [edpp = (2‐aminoethyl)diphenylphosphine] cluster with bases such as NaOH Et N in acetonitrile. For reaction OH – ions, study allowed identification hydroxo species development a procedure synthesis (OH) high yields. This involves substitution coordinated bromide ligands by ligands, associated kinetics is several orders magnitude faster than those Cl , F SCN...
Abstract The novel [W 3 S 4 H (edpp) ] + (edpp=(2‐aminoethyl)diphenylphosphine) ( 1 ) cluster hydride with an acidic −NH 2 functionality has been synthetized and studied. Its crystal structure shows the characteristic incomplete W cubane core outer positions occupied by P N atoms of edpp ligands. Although no signal due to ligands is observed in NMR spectrum, assignment supported H‐ 15 HSQC techniques, changes 31 P{ H} chemical shift, FT‐IR spectra W−H region deuterated D H(edpp) ‐d samples....