A5038632115- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Organometallic Complex Synthesis and Catalysis
- Asymmetric Hydrogenation and Catalysis
- Advanced NMR Techniques and Applications
- Catalytic Alkyne Reactions
- Carbon dioxide utilization in catalysis
- Inorganic Fluorides and Related Compounds
- Crystallography and molecular interactions
- Coordination Chemistry and Organometallics
- Surface Chemistry and Catalysis
- Metal-Organic Frameworks: Synthesis and Applications
- Organoboron and organosilicon chemistry
- Catalytic Cross-Coupling Reactions
University of Bern
2022-2023
University of Oxford
2018-2021
University of York
2020-2021
The non-oxidative catalytic dehydrogenation of light alkanes via C-H activation is a highly endothermic process that generally requires high temperatures and/or sacrificial hydrogen acceptor to overcome unfavorable thermodynamics. This complicated by being such poor ligands, meaning binding at metal centers prior disfavored. We demonstrate biasing the pre-equilibrium alkane binding, using solid-state molecular organometallic chemistry (SMOM-chem), well-defined isobutane and cyclohexane...
Solid/gas single-crystal to (SC-SC) hydrogenation of appropriate diene precursors forms the corresponding σ-alkane complexes [Rh(Cy2P(CH2) nPCy2)(L)][BArF4] ( n = 3, 4) and [ RhH(Cy2P(CH2)2( CH)(CH2)2PCy2)(L)][BArF4] 5, L norbornane, NBA; cyclooctane, COA). Their structures, as determined by X-ray diffraction, have cations exhibiting Rh···H-C σ-interactions which are modulated both chelating ligand identity alkane, while all sit in an octahedral anion microenvironment. These range from η2,η2...
Using solid-state molecular organometallic (SMOM) techniques, in particular solid/gas single-crystal to reactivity, a series of σ-alkane complexes the general formula [Rh(Cy
Donor-flexible ligands are an emerging class of noninnocent ligands. Their ability to adapt their donating strength toward a metal center has had numerous catalytic advantages yet never been utilized stabilize and isolate intermediate complexes within these processes. We demonstrate through the use pincer ligand containing two donor-flexible pyridylidene amide (PYA) arms in coordination with platinum(II) that this adaptability revealed remarkably stable hydride formate complexes. These...
Single-crystal to single-crystal solid-state molecular organometallic (SMOM) techniques are used for the synthesis and structural characterization of σ-alkane complex [Rh(tBu2 PCH2 CH2 PtBu2 )(η2 ,η2 -C7 H12 )][BArF4 ] (ArF =3,5-(CF3 )2 C6 H3 ), in which alkane (norbornane) binds through two exo-C-H⋅⋅⋅Rh interactions. In contrast, bis-cyclohexyl phosphine analogue shows endo-alkane binding. A comparison systems, supported by periodic DFT calculations, NCI plots Hirshfeld surface analyses,...
Gold-based homogeneous catalysis is dominated by redox neutral AuI systems. Redox-active gold-based catalysts are less common, principally because of cycles between and AuIII being hampered unfavorable potentials. We report gold(III) complexes containing pincer-based, donor-flexible pyridylidene amide (PYA) ligands to address these issues. These act as electron reservoirs through two limiting resonance structures consisting either soft, imine coordination sites or harder, zwitterionic...
Vapour-phase surface-initiated cationic polymerisation of ethylvinylether occurs at single-crystals the σ-alkane complex [Rh(Cy2PCH2CH2PCy2)(NBA)][BArF4]. This new surface interface makes these normally very air sensitive materials tolerant to air, while also allowing for onward single-crystal reactivity metal sites within lattice.