A Platinum molecular complex immobilised on the surface of graphene as active catalyst in alkyne hydrosilylation

Abstract A platinum complex bearing a N‐heterocyclic carbene (NHC) ligand functionalised with a pyrene‐tag is immobilised onto the surface of reduced graphene oxide (rGO). The hybrid material composed of an organometallic complex and a graphene derivative is ready available in a single‐step process under mild reaction conditions. This methodology preserves the inherent properties of the active catalytic centre and the support. The platinum hybrid material is an efficient catalyst in hydrosilylation of alkynes and can be recycled and reused for ten runs without significant loss of activity due to its high stability. Interestingly, the catalytic properties of the platinum complex are enhanced after immobilisation onto graphene. The influence of graphene in hydrosilylation of alkynes is discussed

Reduced graphene oxides as carbocatalysts in acceptorless dehydrogenation of N-heterocycles

The catalytic properties of graphene-derived materials are evaluated in acceptorless dehydrogenation of N-heterocycles. Among them, reduced graphene oxides (rGOs) are active (quantitative yields in 23 h) under mild conditions (130 °C) and act as efficient heterogeneous carbocatalysts. rGO exhibits reusability and stability at least during eight consecutive runs. Mechanistic investigations supported by experimental evidence (i.e., organic molecules as model compounds, purposely addition of metal impurities and selective functional group masking experiments) suggest a preferential contribution of ketone carbonyl groups as active sites for this transformation.

Dual role of graphene as support of ligand-stabilized palladium nanoparticles and carbocatalyst for (de)hydrogenation of N-heterocycles

The hybrid material composed of palladium nanoparticles (PdNPs) functionalized with N-heterocyclic carbene ligands (NHCs) immobilized onto the surface of reduced graphene oxide (rGO) results in an efficient catalytic material towards hydrogenation and dehydrogenation of N-heterocycles. The rGO plays a dual role by acting as a carbocatalyst in acceptorless dehydrogenation of N-heterocycles and as a support for the palladium nanoparticles facilitating its interaction with molecular hydrogen turning this hybrid material into an effective hydrogenation catalyst. Hot filtration experiments support the heterogeneous nature of the process underlining the strong interaction of palladium nanoparticles with the graphene enabled by π-interactions of the ligand with the support. The mild conditions used in both transformations of this system without requiring any additives facilitates its potential application in hydrogen storage technologies in the form of liquid organic hydrogen carriers (LOHCs). At the same time, the hybrid material is a robust and efficient catalytic platform that can be recovered and reused up to eight runs in both transformations without significant deactivation. The use of a single solid catalysts that is recyclable in hydrogen conversion and reconversion through (de)hydrogenation of N-heterocycles paves the way for the development of efficient hydrogen storage materials

Reduced Graphene Oxides as Carbocatalysts in Acceptorless Dehydrogenation of N-Heterocycles

[EN] The catalytic properties of graphene-derived materials are evaluated in acceptorless dehydrogenation of N-heterocycles. Among them, reduced graphene oxides (rGOs) are active (quantitative yields in 23 h) under mild conditions (130 degrees C) and act as efficient heterogeneous carbocatalysts. rGO exhibits reusability and stability at least during eight consecutive runs. Mechanistic investigations supported by experimental evidence (i.e., organic molecules as model compounds, purposely addition of metal impurities and selective functional group masking experiments) suggest a preferential contribution of ketone carbonyl groups as active sites for this transformation.Supported by MCIN/AEI/10.13039/501100011033/FEDER (Grant Nos. RTI2018-098237-B-C21, RTI2018-098237-BC22, and PID2019-105881RB-I00), Generalitat Valenciana (No. PROMETEU/2020/028), and Universitat Jaume I (No. UJI-B2018-23).Mollar-Cuni, A.; Ventura-Espinosa, D.; Martin, S.; García Gómez, H.; Mata, JA. (2021). Reduced Graphene Oxides as Carbocatalysts in Acceptorless Dehydrogenation of N-Heterocycles. ACS Catalysis. 11(23):1-6. https://doi.org/10.1021/acscatal.1c04649S16112

Selective Conversion of Various Monosaccharaides into Sugar Acids by Additive‐Free Dehydrogenation in Water

This is the pre-peer reviewed version of the following article: Selective conversion of various monosaccharaides into sugar acids by additive‐free dehydrogenation in water, which has been published in final form at https://doi.org/10.1002/cctc.202000544. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.Abundant sugars of five and six carbon atoms are promising candidates for the production of valuable platform chemicals. Here, we describe the catalytic dehydrogenation of several pentoses and hexoses into their corresponding sugar acids with the concomitant formation of molecular hydrogen. This biomass transformation is promoted by highly active and selective catalysts based on iridium‐(III) complexes containing a triazolylidene as mesoionic carbene ligand (MIC). Monosaccharides are converted into sugar acids in an easy and sustainable manner using only catalyst and water, and in contrast to previously reported procedures, in the absence of any additive. The reaction is therefore very clean, and moreover highly selective, which avoids the tedious purification and product separation. Mechanistic investigations using 1 H NMR and UV‐vis spectroscopies and ESI mass spectrometry (ESI‐MS) indicates the formation of an unprecedented diiridium‐hydride as dormant species that correspond to the catalyst resting state

Stabilization of Nanoparticles Produced by Hydrogenation of Palladium–N-Heterocyclic Carbene Complexes on the Surface of Graphene and Implications in Catalysis

Palladium nanoparticles (NPs) have been obtained by decomposition of well-defined palladium complexes noncovalently anchored onto the surface of reduced graphene oxide. Morphological analysis by microscopy showed the presence of small palladium NPs homogeneously distributed on the support. Characterization by X-ray photoelectron spectroscopy confirmed that palladium NPs contain Pd(2+) and Pd(0) oxidation states and the presence of N-heterocyclic carbene and bromo ligands. The catalytic properties of the NPs with and without the support have been evaluated in the hydrogenation of alkynes. Supported palladium NPs showed increased activity versus the nonsupported ones and could be recycled up to 10 times without the loss of catalytic activity. The composition of the palladium NPs is different for each catalytic cycle indicating a dynamic process and the formation of different catalytic active species. On the contrary, the unsupported palladium NPs showed limited activity caused by decomposition and could not be recycled. The role of the support has been investigated. The results indicate that the support influences the stability of palladium NPs

Supporting Information for Dual role of graphene as support of ligand-stabilized palladium nanoparticles and carbocatalyst for (de)hydrogenation of N-heterocycles

Appendix A. Supplementary data: Multimedia component 1.Peer reviewe

Introducing Catalysis to Undergraduate Chemistry Students: Testing a Ru–NHC Complex in the Selective Dehydrogenative Coupling of Hydrosilanes and Alcohols

This work describes a complete laboratory experiment that involves the synthesis of a ruthenium complex [Ru(p-cym)(NHC)Cl2] (NHC = N-heterocyclic carbene) and its use as a catalyst for the coupling of hydrosilanes and alcohols. The hydrogen gas produced in the reaction is measured using an inverted buret to trap the gas which allows student to monitor the evolution of the reaction. The complete experience constitutes an opportunity to focus on experimental skills and fundamental concepts in organometallic chemistry and catalysis

Introducing Ion Mobility Mass Spectrometry to Identify Site-Selective C–H Bond Activation in N-Heterocyclic Carbene Metal Complexes

The activation of C−H bonds in a selective manner still constitutes a major challenge from a synthetic point of view; thus, it remains an active area of fundamental and applied research. Herein, we introduce ion mobility spectrometry mass spectrometry-based (IM-MS) approaches to uncover site-selective C−H bond activation in a series of metal complexes of general formula [(NHC)LMCl]+ (NHC = N-heterocyclic carbene; L = pentamethylcyclopentadiene (Cp*) or p-cymene; M = Pd, Ru, and Ir). The C−H bond activation at the N-bound groups of the NHC ligand is promoted upon collision induced dissociation (CID). The identification of the resulting [(NHC-H)LM]+ isomers relies on the distinctive topology that such cyclometalated isomers adopt upon site-selective C−H bond activation. Such topological differences can be reliably evidenced as different mobility peaks in their respective CID-IM mass spectra. Alternative isomers are also identified via dehydrogenation at the Cp*/p-cymene (L) ligands to afford [(NHC)(L-H)M]+ . The fragmentation of the ion mobility-resolved peaks is also investigated by CID-IM-CID. It enables the assignment of mobility peaks to the specific isomers formed from C(sp2 )−H or C(sp3 )−H bond activation and distinguishes them from the Cp*/p-cymene (L) dehydrogenation isomers. The conformational change of the NHC ligands upon C−H bond activation, concomitant with cyclometalation, is also discussed on the basis of the estimated collision cross section (CCS). A unique conformation change of the pyrene-tagg