Pt -N-Heterocyclic Carbene Complexes in Solvent-Free Alkene Hydrosilylation.

Herein, we report the catalytic activity of a series of platinum(II) pre-catalysts, bearing N-heterocyclic carbene (NHC) ligands, in the alkene hydrosilylation reaction. Their structural and electronic properties are fully investigated using X-ray diffraction analysis and nuclear magnetic resonance spectroscopy (NMR). Next, our study presents a structure-activity relationship within this group of pre-catalysts and gives mechanistic insights into the catalyst activation step.

Process Development of Heterogeneous Rh Catalyzed Carbene Transfer Reactions Under Continuous Flow Conditions.

A very simple Rh-based catalyst operates under heterogeneous flow conditions for the carbene transfer of methyl diazoacetate (MDA) with several substrates. Two different methods for heterogenizing the catalyst in a column reactor have been applied. Different X-H (X=O, S, Si, CH ) were successfully functionalized by the carbene and cyclopropenation was performed under very mild continuous flow conditions.

Platinum-Catalyzed Alkene Hydrosilylation: Solvent-Free Process Development from Batch to a Membrane-Integrated Continuous Process.

The integration of a membrane separation protocol with the platinum-catalyzed hydrosilylation of olefins is investigated. The catalytic reaction is first optimized in batch where [Pt(IPr*)(dms)Cl ] (IPr*=1,3-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]imidazol-2-ylidene, dms=dimethyl sulfide) demonstrates superior activity compared to the less sterically encumbered [Pt(SIPr)(dms)Cl ] (SIPr=1,3-bis(2,6-diisopropylphenyl)imidazolidine) congener. Filtration conditions are identified in membrane screening experiments.

Dinuclear gold(i) complexes: from bonding to applications.

The last two decades have seen a veritable explosion in the use of gold(i) complexes bearing N-heterocyclic carbene (NHC) and phosphine (PR) ligands. Both ligand families have significantly contributed to the stability and design of a plethora of gold complexes. Design is oftentimes associated with application.

Straightforward access to chalcogenoureas derived from N-heterocyclic carbenes and their coordination chemistry.

Chalcogen-based urea compounds supported by a wide range of N-heterocyclic carbenes are synthesised and fully characterised. Coordination of selenoureas is further explored with Group 11 transition metals to form new copper, gold and silver complexes. Single crystal X-ray analyses unambiguously establish the solid-state coordination of these complexes and show that the geometry of a complex is highly influenced by a combination of electronic properties - mainly π-accepting ability - and steric hindrance of the ligands, as well as the nature of the metal, affording a variety of coordination behaviours.