A5047606297- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Catalytic Cross-Coupling Reactions
- Organoboron and organosilicon chemistry
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Organometallic Complex Synthesis and Catalysis
- Coordination Chemistry and Organometallics
- Ammonia Synthesis and Nitrogen Reduction
- Nanomaterials for catalytic reactions
- Synthetic Organic Chemistry Methods
- Asymmetric Hydrogenation and Catalysis
- Carbon dioxide utilization in catalysis
- Catalytic Processes in Materials Science
- Synthesis and characterization of novel inorganic/organometallic compounds
University of Bath
2021-2025
Ball milling of 5-, 6-, and 7-membered N-heterocyclic carbene (NHC) salts, copper( i ) chloride alkali metal bases including alkoxides, amides, organolithium produces to 12 NHC-copper complexes in moderate good yields.
Abstract Copper is ubiquitous as a structural material, and reagent in (bio)chemical transformations. A vast number of chemical reactions rely on the near-inevitable preference copper for positive oxidation states to make useful compounds. Here we show this electronic paradigm can be subverted stable compound with copper-magnesium bond, which conforms formal state Cu(-I). The Cu-Mg bond synthesized by reaction an N-heterocyclic carbene (NHC) ligated alkoxide dimeric magnesium(I) compound....
Abstract σ‐Bond metathesis reactions between [(6‐Dipp)CuOtBu] (6‐Dipp=:C({Dipp}NCH 2 ) CH , Dipp=2,6‐iPr −C 6 H 3 and three diboranes gave access to new copper(I) boryl complexes [(6‐Dipp)CuBcat], [(6‐Dipp)CuBneop], [(6‐Dipp)CuBhex] (cat=1,2‐O C 4 ; neop=(OCH C(CH hex=OC(CH )HCH O). Whilst [(6‐Dipp)CuBcat] [(6‐Dipp)CuBneop] formed rapidly in toluene, required heating 60 °C for days. The were characterised by single‐crystal X‐ray crystallography which showed all cases that the systems...
Reaction of bis(pinacolato)diboron with (6-Dipp)CuOtBu generates a ring-expanded N-heterocyclic carbene supported copper(I) boryl, (6-Dipp)CuBpin. This compound showed remarkable stability and was characterised by NMR spectroscopy X-ray crystallography. (6-Dipp)CuBpin readily dechalcogenated range heterocumulenes such as CO2, isocyanates isothiocyanates to yield (6-Dipp)CuXBpin (X = O, S). In the case CO2 catalytic reduction CO is viable in presence excess bis(pinacolato)diboron. contrast,...
Four N-heterocyclic carbene (NHC) supported copper( i ) germyls have been synthesised containing both normal- and ring-expanded NHCs. Their π-insertion σ-bond metathesis chemistry has explored in stoichiometric catalytic regimes.
Reaction of (6-Dipp)CuOtBu (6-Dipp=C{NDippCH
Three ring-expanded N-heterocyclic carbene-supported copper(I) triphenylstannyls have been synthesised by the reaction of (RE-NHC)CuOtBu with triphenylstannane (RE-NHC = 6-Mes, 6-Dipp, 7-Dipp). The compounds were characterised NMR spectroscopy and X-ray crystallography. Reaction (6-Mes)CuSnPh3 di-p-tolyl carbodiimide, phenyl isocyanate phenylisothiocyanate gives access to a benzamidinate, benzamide benzothiamide respectively via transfer from triphenylstannyl anion concomitant formation...
Frustrated Lewis pairs (FLPs) have evolved from a revolutionary concept to widely applied catalysts. We recently reported the ring-expanded N-heterocyclic carbene supported copper(I) boryliminomethanide, (6-Dipp)CuC(=NtBu)Bpin and noted it reacted with heterocumulenes in fashion reminiscent of FLPs. thus set out explore its reactivity range other substrates known react This was undertaken by series synthetic studies using NMR spectroscopy, mass spectrometry, IR single crystal X-ray...
<title>Abstract</title> A vast number of chemical reactions rely on the near-inevitable preference copper for positive oxidation states to make useful compounds. In this work, we report that reaction an N-heterocyclic carbene (NHC) ligated alkoxide with a dimeric magnesium(I) compound results in stable copper-magnesium bond, which conforms formal state Cu(-I). Single crystal X-ray crystallography and quantum calculations further support assignment sub-zero at copper. The Cu-Mg bond acts as...
Two new model complexes function as electrochemical probes for the evaluation of electronic properties N-heterocyclic carbene ligands. The linear ones unearth flaws previous when evaluating most sterically demanding NHCs.
Abstract A process for the catalytic reduction of nitrous oxide using NHC‐ligated copper(I) tert ‐butoxide precatalysts and B 2 pin as reductant is reported. These reactions proceed under mild conditions via copper(I)‐boryl intermediates which react with N O by facile O‐atom insertion into Cu−B bond liberate . Turnover numbers >800 can be achieved at 80 °C 1 bar O.
Abstract A process for the catalytic reduction of nitrous oxide using NHC‐ligated copper(I) tert ‐butoxide precatalysts and B 2 pin as reductant is reported. These reactions proceed under mild conditions via copper(I)‐boryl intermediates which react with N O by facile O‐atom insertion into Cu−B bond liberate . Turnover numbers >800 can be achieved at 80 °C 1 bar O.