This review highlights the use of a bisphosphine ligand group in homogeneous catalysis. This ligand group is known as the Xantphos-like ligands, which are based on the generic formula of 2,2′-bis(phosphino)diaryl ether. The synthesis of the main members is summarized and emphasis is given to ligands that can be easily synthesized, also on large scale. The catalytic applications are not comprehensively presented, but instead, about 20% of the examples from literature have been extracted, aiming at the demonstration of diversity, peculiar examples, historical development, design vs. trial and error, and new reactions. Metals ranging from group 7 to 11 have been used in a wide variety of reactions: hydroformylation, alkoxycarbonylation, hydrocyanation, cross-coupling reactions for many C–C and C–X bond forming reactions, carbonylative coupling reactions, phosphinations, etc.

Magnetically induced catalysis in solution for the valorization of biomass-derived compounds using FeNi ₃ @Ni nanoparticles.

Secondary phosphine oxides (SPOs) can be used as ligands to stabilize catalytically active gold nanoparticles (AuNPs). These materials are active and very selective in the chemoselective hydrogenation of acrolein and other α,β-unsaturated aldehydes, but the origin of the activity remains elusive. Here, by means of density functional theory, we identify a cooperative effect at the AuNP–SPO interface that enables the heterolytic cleavage of the H₂ molecule and its kinetically favorable concerted addition to the C═O bond (in a transfer hydrogenation-like mode) to form the corresponding allyl alcohol. From the mechanism it is possible to identify the descriptors that explain the activity for a family of SPO-stabilized AuNPs and a set of unsaturated aldehydes. The activity depends on the basicity difference between ligand and reactant and the sites available on the nanoparticle.

Ligand control of metal nanoparticles (MNPs) is rapidly gaining importance as ligands can stabilize the MNPs and regulate their catalytic properties. Herein we report the first example of Pt NPs ligated by imidazolium-amidinate ligands that bind strongly through the amidinate anion to the platinum surface atoms. The binding was established by ¹⁵N NMR spectroscopy, a precedent for nitrogen ligands on MNPs, and XPS. Both monodentate and bidentate coordination modes were found. DFT showed a high bonding energy of up to −48 kcal mol⁻¹ for bidentate bonding to two adjacent metal atoms, which decreased to −28 ± 4 kcal mol⁻¹ for monodentate bonding in the absence of impediments by other ligands. While the surface is densely covered with ligands, both IR and ¹³C MAS NMR spectra proved the adsorption of CO on the surface and thus the availability of sites for catalysis. A particle size dependent Knight shift was observed in the ¹³C MAS NMR spectra for the atoms that coordinate to the surface, but for small particles, ∼1.2 nm, it almost vanished, as theory for MNPs predicts; this had not been experimentally verified before. The Pt NPs were found to be catalysts for the hydrogenation of ketones and a notable ligand effect was observed in the hydrogenation of electron-poor carbonyl groups. The catalytic activity is influenced by remote electron donor/acceptor groups introduced in the aryl-N-substituents of the amidinates; p-anisyl groups on the ligand gave catalysts several times faster the ligand containing p-chlorophenyl groups.