Reversible carbon monoxide binding at copper(I) P–S–X (X = N, O) coordination polymers

Reaction of Ph2PCH2CH2S(2-C6H4NH2) (1) or Ph2PCH2CH2S(2-C6H4OMe) (2) with CuCl and AgSbF6 in the presence of THF affords {[Cu(1)THF](SbF6)}n (3) and {[Cu(2)THF](SbF6)}n (4). In the solid state, THF-inclusive 3 exists as a one dimensional zigzag coordination polymer in which each P–S–N ligand is connected to two copper(I)-centres. Both 3 and 4 are able to bind CO reversibly in solution or can be desolvated at 110 °C in vacuo to give {[Cu(1)](SbF6)}n (7) and {[Cu(2)](SbF6)}n (8). These solvent-free compounds have been found to bind carbon monoxide reversibly over multiple cycles in solution and in the solid state, under mild conditions.

New tridentate P–S–N donor ligands can bridge two adjacent copper(I) centres to form one-dimensional ‘zig-zag’ coordination polymers. Under relatively mild conditions, these polymers can reversibly bind CO in solution and in the solid state.Figure optionsDownload as PowerPoint slideHighlights
► Copper(I) coordination polymers containing P–S–N or P–S–O ligands have been prepared.
► These compounds can bind carbon monoxide reversibly in solution and in the solid state.
► It is possible to desolvate the THF-inclusive polymers at 110 °C in vacuo.