ABSTRACT
Carboxylate-assisted Pd-catalyzed C-H bond activation constitutes a mild and versatile synthetic tool to efficiently and selectively cleave inert C-H bonds. Herein, we demonstrate a simple method to experimentally evaluate both reactivity and selectivity in such systems using mass spectrometry (MS) methods. The N-heterocyclic carbene (NHC) cations [(NHC)PdX]+, bearing as X- ligand bases commonly used to promote the C-H activation (carboxylates and bicarbonate), are generated in the gas-phase by ESI-MS. Their C-H bond activation at the N-bound groups of the NHC is then studied using Collision Induced Dissociation (CID) experiments. Ion Mobility Spectrometry (IM)-MS is exploited to identify a number of regioisomers associated with the distinctive site selective C-H activations. It is demonstrated that such C-H activation concomitant with acetic acid release occurs from a mixture of activated [(NHC-H)Pd(CH3CO2H)]+ and non-activated [(NHC)Pd(CH3CO2)]+ complexes. The identity of the X-type ligands (X = Cl-, carboxylates and bicarbonate) has a significant impact on the regioisomer branching ratio upon CID conditions. IM-MS in conjunction with a DFT mechanistic study is presented for the acetate-assisted C-H activation of the [(NHC)Pd(CH3CO2)]+ cation featuring butyl and aryl as N-donor groups.
ABSTRACT
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-tagged NHC members is identified that involves the reorientation of the NHC ring accompanied by a folding of the pyrene moiety.
ABSTRACT
An effective visible-light-promoted iridium(III)-catalyzed hydrogen production from N-heterocycles is described. A single iridium complex constitutes the photocatalytic system playing a dual task, harvesting visible-light and facilitating C-H cleavage and H2 formation at room temperature and without additives. The presence of a chelating C-N ligand combining a mesoionic carbene ligand along with an amido functionality in the IrIII complex is essential to attain the photocatalytic transformation. Furthermore, the IrIII complex is also an efficient catalyst for the thermal reverse process under mild conditions, positioning itself as a proficient candidate for liquid organic hydrogen carrier technologies (LOHCs). Mechanistic studies support a light-induced formation of H2 from the Ir-H intermediate as the operating mode of the iridium complex.
