Rémy Brousses

Bio: Rémy Brousses is an academic researcher from University of Toulouse. The author has contributed to research in topics: Carbene & Malonate. The author has an hindex of 9, co-authored 11 publications receiving 472 citations. Previous affiliations of Rémy Brousses include Centre national de la recherche scientifique & University of Rennes.

Hydrosilylation of Aldehydes and Ketones Catalyzed by Half‐Sandwich Manganese(I) N‐Heterocyclic Carbene Complexes

Abstract: Easily available manganese(I) N-heterocyclic carbene (NHC) complexes, Cp(CO)2MnACHTUNGTRENNUNG(NHC), obtained in one step from industrially produced cymantrene, were evaluated as pre-catalysts in the hydrosilylation of carbonyl compounds under UV irradiation. Complexes with NHC ligands incorporating at least one mesityl group led to the most active and selective catalytic systems. A variety of aldehydes (13 examples) and ketones (11 examples) were efficiently reduced under mild conditions [Cp(CO)2Mn ACHTUNGTRENNUNG(IMes) (1 mol%), Ph2SiH2 (1.5 equiv.), hn (350 nm), toluene, 25 8C, 1–24 h] with good functional group tolerance.

A Stable but Highly Reactive Phosphine‐Coordinated Borenium: Metal‐free Dihydrogen Activation and Alkyne 1,2‐Carboboration

Abstract: Borenium cations have been found to be valuable analogues of boranes as a result of their cationic character which imparts high electrophilicity. Herein, we report the synthesis, characterization, and reactivity of a new type of borenium cation employing a naphthyl bridge and a strong intramolecular P→B interaction. The cation reacts with H2 in the presence of PtBu3 (frustrated Lewis pair (FLP) approach) but also on its own. The mechanism of the reaction between the borenium cation and H2 in the absence of PtBu3 has been investigated using deuterium-labeling experiments and DFT calculations. Both experiments and calculations imply the side-on coordination of H2 to the B center, followed by heterolytic splitting and BC bond cleavage. An uncommon syn 1,2-carboboration has also been observed upon reaction of the borenium ion with 3-hexyne.

Cationic gold(III) alkyl complexes: generation, trapping, and insertion of norbornene.

Abstract: Migratory insertion of alkenes into gold–carbon bonds, a fundamental yet unprecedented organometallic transformation, has been investigated from a discrete (P,C) cyclometalated gold(III) dimethyl complex. Methide abstraction by B(C6F5)3 is shown to generate a highly reactive cationic AuIII complex that evolves spontaneously by C6F5 transfer from boron. In the presence of norbornene, migratory insertion into the AuC bond proceeds readily. The resulting norbornyl complex is efficiently trapped with pyridines or chloride to give stable four-coordinate adducts.

Quantifying and understanding the electronic properties of N-heterocyclic carbenes

Abstract: The use of N-heterocyclic carbenes (NHCs) in chemistry has developed rapidly over the past twenty years. These interesting compounds are predominantly employed in organometallic chemistry as ligands for various metal centres, and as organocatalysts able to mediate an exciting range of reactions. However, the sheer number of NHCs known in the literature can make the appropriate choice of NHC for a given application difficult. A number of metrics have been explored that allow the electronic properties of NHCs to be quantified and compared. In this review, we discuss these various metrics and what they can teach about the electronic properties of NHCs. Data for approximately three hundred NHCs are presented, obtained from a detailed survey of the literature.

Smart N-Heterocyclic Carbene Ligands in Catalysis

Abstract: It is well-recognized that N-heterocyclic carbene (NHC) ligands have provided a new dimension to the design of homogeneous catalysts. Part of the success of this type of ligands resides in the limitless access to a variety of topologies with tuned electronic properties, but also in the ability of a family of NHCs that are able to adapt their properties to the specific requirements of individual catalytic transformations. The term “smart” is used here to refer to switchable, multifunctional, adaptable, or tunable ligands and, in general, to all those ligands that are able to modify their steric or electronic properties to fulfill the requirements of a defined catalytic reaction. The purpose of this review is to comprehensively describe all types of smart NHC ligands by focusing attention on the catalytically relevant ligand-based reactivity.

Electronic Properties of N-Heterocyclic Carbenes and Their Experimental Determination

Abstract: N-Heterocyclic carbenes (NHCs) have become without doubt one of the most exciting and popular species in chemical science due to the ease of their preparation and modularity in stereoelectronic properties. Numerous types of NHCs have been prepared, and various experimental methodologies have been proposed for the study of their electronic properties in order to rationalize reactivities observed. The objective of this article is to provide a comprehensive overview of the most common and popular ones among them. In particular, these include the nickel(0)-based TEP, its rhodium(I) and iridium(I) variants, LEP and related electrochemical methods, the palladium(II)-based HEP, phosphinidene- and selenourea-based methods, as well as the use of direct 1J(C–H) coupling constants of the precarbene carbon in azolium salts. Each individual method and the underlying principle of detection it utilizes will be critically discussed in terms of strength and weakness. In addition, comprehensive amounts of data from various...