A5068147047- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Catalytic Cross-Coupling Reactions
- Organometallic Complex Synthesis and Catalysis
- Asymmetric Hydrogenation and Catalysis
- Synthesis and Catalytic Reactions
- Organoboron and organosilicon chemistry
- Catalytic C–H Functionalization Methods
- Radical Photochemical Reactions
- Coordination Chemistry and Organometallics
- Carbon dioxide utilization in catalysis
- Sulfur-Based Synthesis Techniques
- Cyclopropane Reaction Mechanisms
- TiO2 Photocatalysis and Solar Cells
- Asymmetric Synthesis and Catalysis
- Catalytic Alkyne Reactions
- Fluorine in Organic Chemistry
- Crystallography and molecular interactions
- Nanoparticles: synthesis and applications
- Oxidative Organic Chemistry Reactions
- Chemical Synthesis and Reactions
- Free Radicals and Antioxidants
- Ionic liquids properties and applications
- Advanced Photocatalysis Techniques
- Metal-Organic Frameworks: Synthesis and Applications
Heriot-Watt University
2021-2024
Heriot-Watt University Malaysia
2024
University of Manchester
2024
University of the Basque Country
2015-2023
Ayuntamiento de San Sebastián
2019-2021
Faculty (United Kingdom)
2019
University of Alicante
2015
Highly distorted polycyclic aromatic hydrocarbons (PAHs) are predicted to be attractive goals in nanoscience owing the new properties they can exhibit. We have shown that a variety of functionalized heptagon-containing nanographenes easily prepared from simple building blocks by sequence Co-catalyzed cyclotrimerization and cyclodehydrogenation reactions. The versatility this strategy allows easy subsequent enlargement these nanostructures Ni-catalyzed cross-coupling final Soluble extended 1...
Abstract Cationic pyridiniophosphine ligands have been synthetized in an attempt to develop a deep eutectic solvents (DESs) compatible catalytic systems. These ligands, combination with PdCl 2 , successfully applied different palladium‐catalyzed cross coupling reactions, such as Suzuki–Miyaura, Sonogashira, or Heck couplings. While traditional palladium DES medium failed reproduce the results obtained VOC solvents, these cationic phosphines improved activity of no other ligand could polar...
[(NacNac)Zn(DMT)][B(C6F5)4], 1, (NacNac = {(2,6- i Pr2H3C6)N(CH3)C}2CH), DMT N,N-dimethyl-4-toluidine), was synthesized via two routes starting from either (NacNac)ZnEt or (NacNac)ZnH. Complex 1 is an effective (pre)catalyst for the C-H borylation of (hetero)arenes using catecholborane (CatBH) with H2 only byproduct. The scope included weakly activated substrates such as 2-bromothiophene and benzothiophene. Computational studies elucidated a plausible reaction mechanism that has overall free...
The air tolerant precatalyst, [Rh(L)(NBD)]Cl ([1]Cl) [L = κ3-(iPr2PCH2CH2)2NH, NBD norbornadiene], mediates the selective synthesis of N-methylpolyaminoborane, (H2BNMeH)n, by dehydropolymerization H3B·NMeH2. Kinetic, speciation, and DFT studies show an induction period in which active catalyst, Rh(L)H3 (3), forms, sits as outer-sphere adduct 3·H3BNMeH2 resting state. At end catalysis, dormant Rh(L)H2Cl (2) is formed. Reaction 2 with H3B·NMeH2 returns 3, alongside proposed formation boronium...
The dehydropolymerization of H3B·NMeH2 to form N-methylpolyaminoborane using neutral and cationic catalysts based on the {Ir( i Pr-PNHP)} fragment [ Pr-PNHP = κ3-(CH2CH2P Pr2)2NH] is reported. Neutral Ir( Pr-PNHP)H3 or Pr-PNHP)H2Cl precatalysts show no, poor unselective, activity respectively at 298 K in 1,2-F2C6H4 solution. In contrast, addition [NMeH3][BArF4] (ArF 3,5-(CF3)2C6H3) immediately starts catalysis, suggesting that a catalytic manifold operates. Consistent with this,...
A combined experimental and computational study of the structure reactivity two [RuZn
The syntheses, reactivity and electronic structure analyses of [Ru(PPh
DFT studies reveal the distinct fates of 1,2- and 1,3-acetate migration in cycloisomerization reaction 1,5-enynes significant differences between platinum(<sc>ii</sc>) gold(<sc>i</sc>) catalysis.
Simple treatment of chiral titanium(IV) enolates with diacyl peroxides produces highly diastereoselective decarboxylative alkylations to efficiently deliver the corresponding adducts, most which are not accessible through any current alkylating procedures. Such an unprecedented alkylation proceeds SET process that triggers decomposition peroxide into a carbon-centered radical finally combines resulting Cα radical. The procedure has been applied enantioselective synthesis arundic acid.
C−H metalation is the most efficient method to prepare aryl–zinc and –aluminum complexes that are highly useful nucleophiles. Virtually all C–H routes form Al or Zn organometallic reagents require stoichiometric, strong Brønsted bases with no base-catalyzed reactions reported, our knowledge. Herein we present a catalytic process aryl-zinc aryl-aluminum uses only simple amine (e.g., Et3N) in sub-stoichiometric quantity (10 mol%). Key this approach coupling an endergonic step using...
The reaction of [Ir(IPr)2H2][BArF4] (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BArF4 B{C6H3(3,5-CF3)2}4) with ZnMe2 proceeds CH4 elimination to give [Ir(IPr)(IPr′)(ZnMe)2H][BArF4] (3, where (IPr′) is a cyclometalated ligand). 3 reacts H2 form tetrahydride [Ir(IPr)2(ZnMe)2H4][BArF4], 4, that loses under forcing conditions [Ir(IPr)2(ZnMe)2H2][BArF4], 5. Crystallization also results in the formation its noncyclometalated isomer, [Ir(IPr)2(ZnMe)2][BArF4], 2, solid state....
The reactivity of the Ir(I) PONOP pincer complex [Ir(iPr-PONOP)(η2-propene)][BArF4], 6, [iPr-PONOP = 2,6-(iPr2PO)2C6H3N, ArF 3,5-(CF3)2C6H3] was studied in solution and solid state, both experimentally, using molecular density functional theory (DFT) periodic-DFT computational methods, as well situ single-crystal to (SC-SC) techniques. Complex 6 is synthesized from sequential addition H2 propene, then application vacuum, [Ir(iPr-PONOP)(η2-COD)][BArF4], 1, a reaction manifold that proceeds...
A protocol for the Pd(II)-catalyzed C-H alkenylation reaction of substituted N-allylanilines via an unusual 6-endo process has been developed. density functional theory (DFT) study mechanistic pathway shown that coordination remote protecting group to palladium center is determinant control regioselectivity in favor process. The would proceed prior activation alkene. This procedure constitutes a mild and efficient method synthesis 1,4-dihydroquinoline derivatives from simple readily...
A range of functionalized heteroaromatic boronic acid derivatives are readily accessed by a diboration/6π-electrocyclization sequence. This study revealed the surprising observation that there is direct relationship between oxime ether stereochemistry and reactivity towards electrocyclization. Specifically, E-oxime ethers found to be significantly more reactive than their Z-counterparts (stereochemistry relative azatriene scaffold). In contrast, configuration at alkene terminus has little...
1,2,6-Thiadiazines treated with visible light and 3O2 under ambient conditions are converted into difficult-to-access 1,2,5-thiadiazole 1-oxides (35 examples, yields of 39-100%). Experimental theoretical studies reveal that 1,2,6-thiadiazines act as triplet photosensitizers produce 1O2 then undergo a chemoselective [3 + 2] cycloaddition to give an endoperoxide ring contracts selective carbon atom excision complete economy. The reaction was optimized both batch continuous-flow is also...
A completely regioselective and highly stereoselective palladium-catalyzed intramolecular hydroarylation of arenesulfonyl ynamines to benzothiazoles was developed. The presence an electron-withdrawing group on the triple bond sulfonyl ynamine crucial for success reaction our mechanistic studies suggest alkyne-directed 5-
Group 2 organometallics were synthesised with a thiopyridyl scorpionate ligand and tested for their catalytic activity in hydrophosphination reactions. Kinetic studies DFT calculations also used to elucidate degradation pathways.
Abstract C−H metalation is the most efficient method to prepare aryl–zinc and –aluminium complexes that are ubiquitous nucleophiles. Virtually all routes form Al/Zn organometallics require stoichiometric, strong Brønsted bases with no base‐catalyzed reactions reported. Herein we present a catalytic in amine/ammonium salt (Et 3 N/[(Et N)H] + ) process aryl‐zinc aryl‐aluminium complexes. Key this approach coupling an endergonic step sufficiently exergonic dehydrocoupling between ammonium...
Abstract C−H metalation is the most efficient method to prepare aryl–zinc and –aluminium complexes that are ubiquitous nucleophiles. Virtually all routes form Al/Zn organometallics require stoichiometric, strong Brønsted bases with no base‐catalyzed reactions reported. Herein we present a catalytic in amine/ammonium salt (Et 3 N/[(Et N)H] + ) process aryl‐zinc aryl‐aluminium complexes. Key this approach coupling an endergonic step sufficiently exergonic dehydrocoupling between ammonium...
The unexpected metal free synthesis of trifluoromethyl arenes is described. It involved un unprecedented formal [3 + 3] cycloaromatization reaction dicyanoalkenes and conjugated fluorinated <italic>tert</italic>-butyl sulfinyl imines in the presence DBU.
Abstract The syntheses, reactivity and electronic structure analyses of [Ru(PPh 3 ) 2 (ZnMe) 4 H ], 1 a , (ZnPh) b are reported. exhibits an 8‐coordinate Ru centre with axial phosphines symmetrical (2 : 2) arrangement ZnMe ligands in the equatorial plane. undergo facile, sequential exchange ZnPh to give which shows ligands. Both exist equilibrium their respective isomers. Mechanisms for ZnMe/ZnPh isomerisation proposed using DFT calculations. relationships these {Ru(ZnR) } species...
Interactions between polycyclic aromatic hydrocarbons (PAHs) and titanium dioxide (TiO2) nanoparticles (NPs) can produce unforeseen photoproducts in the aqueous phase. Both PAHs TiO2-NPs are well-studied highly persistent environmental pollutants, but consequences of PAH-TiO2-NP interactions rarely explored. We investigated PAH photoproduct formation over time for benzo[a]pyrene (BaP), fluoranthene (FLT), pyrene (PYR) presence ultraviolet A (UVA) using a combination analytical computational...