Supramolecular Construction of Bidentate Ligands Through Self‐assembly by Hydrogen Bonding

Hydroxypyridine/Pyridone Interconversions within Ruthenium Complexes and Their Application in the Catalytic Hydrogenation of CO2

“…Reaction of any of the [2] + complexes with one equivalent of DBU in THF yielded complex 3, as indicated by a new 31 P{ 1 H} NMR resonance at −4.8 ppm (Scheme 4). With a new product observed, the reaction was carried out on a preparative scale.…”

“…This was later developed and investigated further within the complex [ cis -PtCl 2 ( 6-DPPon ) 2 ] (Scheme , top right) . These examples illustrated the concept of flexible dynamic pseudo-bidentate ligand motifs generated via hydrogen bonding from two monodentate phosphine binding sites . In the case of the “( 6-DPPon ) 2 ” ligand, the bite angle was found to be 105° .…”

“…6 These examples illustrated the concept of flexible dynamic pseudobidentate ligand motifs generated via hydrogen bonding from two monodentate phosphine binding sites. 1 In the case of the "(6-DPPon) 2 " ligand, the bite angle was found to be 105°. 6 In the solid state, the 6-DPPon ligand also exists as a dimer through hydrogen bonding (Scheme 1, top middle).…”

“…Noncovalent interactions between ligands in the secondary sphere offer a new way to modulate the stereoelectronic properties of the metal center and introduce new modes of reactivity. This is evident in ligands that organize themselves through hydrogen bonding and have found extensive applications in catalytic transformations. , They are known to provide lower-energy alternative reaction pathways to reduce the activation energies via hydrogen bonding and to help solubilize complexes in polar solvents. One such ligand motif that has demonstrated such potential is the 2-pyridyl-substituted phosphine ligand 6-diphenylphosphino-2-pyridone ( 6-DPPon ) , (Scheme , top).…”