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Overall, NOHCs were found to be rather weakly donating carbenes.

I have obtained my undergraduate education from the University of Bern from 1991 to 1996 and subsequently moved to the Netherlands for graduate studies under the supervison of Gerard van Koten at Utrecht University. In a truly fantastic research environment I completed my PhD thesis in 2000 on the development of new sensors, switches, and catalysts derived from late transition metal pincer complexes. The thesis was later awarded the Bakker price from the Royal Dutch Society of Chemistry. I then joined the group of Robert H. Crabtree at Yale as postdoctoral fellow, working on carbene ligands for bond activation, which was a hugely influential period in terms of chemistry and beyond. In mid 2002, I relocated back to Europe and was employed by Ciba SC (Basel, Switzerland) as a postdoctoral researcher working on nanoparticles for coating effects in an industrial environment. In 2003, I returned to academia and launched my independent research as an Alfred Werner Assistant Professor at the University of Fribourg (Switzerland). During that time, I have also been a visiting professor with Sally Brooker at Otago University (New Zealand), and I received an ERC Starting Grant. In 2009, I join the faculty at University College Dublin as full professor. The Dublin time stood out for the many great colleagues I met, the modern infrastructure, and above all the enthusiastic and dedicated research team that our group has become. Our research achievements have been recognized during that period by a Humboldt research award (Bessel Fellowship), by a distinction from the Catalysis Society of South Africa (CATSA eminent visitor), and by an ERC Consolidator Grant. In 2014, I accepted a call from my alma mater and since summer 2015 , I am back in Switzerland as Professor of Inorganic Chemistry. I am fortunate enough that the entire research team joined me in relocating to Bern, where we have brand new labs that suit us perfectly. Throughout these years and to date, I have been privileged and proud to have been part of a fantastic research team, and to have been supported (and challenged) by most inspiring collaborators around the globe.

Outside my chemistry life, I enjoy family life, spending time in the mountains, all types of sports activities, and traveling to meet colleagues and friends.

Synthesis, characterization and luminescence studies of gold(I)-NHC amide complexes.

The structure of one of these was determined by single-crystal diffraction study and consists of a square-planar coordination around the palladium center where the NHC ligand is trans to the amine of the palladacycle.

T1 - Synthesis of a new chiral C2-symmetric NHC-AuCl complex

“Synthesis, Characterization, and Structure of [GaCl3(NHC)] Complexes.”  26 (13): 3256–3259.

Inspired by the tautomeric relationship of imidazole and N-heterocyclic carbenes, we have been intrigued about the implications of such carbenes in metalloenzymes. Enzymes are the machinery of all biological transformations, and provide inspiration for designing artificial catalysts. New insights into the mode of action of enzymes is therefore instrumental for developing more competent synthetic catalysts as well as for better understanding natural systems. In collaboration with F. Paradisi (U Nottingham), we have begun to explore carbene binding to metalloenzymes. We have been focusing on blue copper proteins such as azurin and specific mutants of azurin to investigate the possibility of carbene bonding to the copper center, and to evaluate the effect that such bonding entails. While azurin is predominantly involved in electron transfer processes through reversible copper(II) reduction and oxidation, other blue copper proteins are catalytically active in redox transformations of substrates. Hence, these enzymes provide an attractive probe to explore the relevance of carbene bonding on the catalytic performance of the enzyme.

AB - A New chiral C2 symmetric NHC ligand with two binaphthyl units has been synthesized. The new NHC ligand features two seven-membered rings that link the imidazolylidene with the binaphthyl units. X-Ray crystallographic analysis of the new NHC-AuCl complex indicates that the Au-Cl bond is located between the phenyl groups of the binaphthyl units and suggests that this arrangement could induce enantioselectivity in reactions. Indeed, catalytic asymmetric ene-yne cyclization of 2b in the presence of a catalytic amount (5 mol%) of cationic complex of 13 quantitatively afforded the cyclized product with 78% ee.

The σ-lone pair at the divalent carbon is the HOMO of these species.

“Synthesis, Characterization, and Structure of [GaCl3(NHC)] Complexes.”  26.13 (2007): 3256–3259.

The influence of the 15 bidentate ligands L2 on the 13Ccarbene signals of the iPr2-bimy reporter ligand in the chelate complexes was studied, on the basis of which a facile methodology for the donor strength determination of bidentate ligands was developed.

During the characterization of the gold–NHC amide complexes we observed that some of the complexes possessed luminescent properties when exposed to ultraviolet light (λ = 366 nm) in the solid state ().

Overall, mixed dicarbene/diphosphine complex 3 showed the best catalytic performance.
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Synthesis of imidazole-based NHC–Au(I) complexes and …

Triazolylidene silver complexes are precursors of highly active catalysts for oxazoline formation via aldol condensation. The catalytic performance mirrors that of gold carbene species that are activated with Ag+, suggesting a retro-transfer of the carbene from Au to Ag.

Publications – N-Heterocyclic Carbenes

We are fascinated by the diversity of effects that ligands can have to instigate new properties in transition metal complexes and we are therefore strongly interested in designing and developing new ligands that impart specific properties to the metal center. One of these ligands are triazolylidenes, a mesoionic carbene that we discovered in 2008. This ligand offers various opportunities for catalysis, including strong electron donor properties, a high synthetic flexibility that allows for a wide variety of functional and chelating groups to be incorporated, and a high polarity, which imparts solubility in water and other polar media. We have obtained evidence in a variety of catalytic reactions like nickel-catalysed hydrosilylation, ruthenium-catalyzed alcohol dehydrogenation, or iridium-catalyzed water oxidation, that the triazolylidene ligand scaffold is controlling the reactivity of the coordinated metal center. Because of the synthetic versatility and the easy accessibility of the ligand, tailoring of the ligand properties is straightforward and we have disclosed improved catalytic activity by ligand tuning. More recently, we have discovered a straightforward approach to functionalize the ligand on the complex as opposed to the more traditional approach of preparing a functional ligand and only then install the metal center. This approach gives rapid access to a large diversity of functionalized ligands in a very last step, and to ligand scaffolds that are not accessible by traditional routes.

Transition metal carbene complex - Wikipedia

Triazolylidene silver complexes are precursors of highly active catalysts for oxazoline formation via aldol condensation. The catalytic performance mirrors that of gold carbene species that are activated with Ag+, suggesting a retro-transfer of the carbene from Au to Ag.

A transition metal carbene complex is an organometallic compound ..

This article accounts for the most recent one developed by the Huynh group, which employs 13C NMR spectroscopy to determine ligand donor strengths using N-heterocyclic carbene complexes.

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