Bisxantphos: Stereoselective synthesis and coordination behaviour of a new class of cyclic double bridged diphosphines

A new class of cyclic double bridged diphosphine ligands was developed and the coordination properties are described. The reaction of 4,5-dilithioxanthene with dichlorophenylphosphine gave a cyclic double bridged diphosphine ligand based on two xanthene backbones (4) as a single stereoisomer. X-ray crystal structure determination revealed that the groups bridging the two phosphorus atoms are arranged in a syn-disposition. This new cyclic bisxantphos structure was modified with bulky residues at the third substituent of the phosphorus atoms, thus forming cavity-shaped ligands.

Graphical abstractA new cyclic bisxantphos structure was modified with bulky residues at the third substituent of the phosphorus atoms, thus forming cavity-shaped ligands.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Double bridged diphosphines based on two xanthene backbones were prepared. ► Metal embracement of these ligands is particularly effective. ► Bulky residues at the phosphorus atoms result in cavity-shaped ligands.