Diarylformamides as a Safe Reservoir and Room Temperature Source of Ultra-Pure CO in the Context of a 'Green' rWGS Reaction.

Diphenylformamide 1 and bisformamide 9 are shown to be safe reservoirs and sources of CO. Their perfectly selective decarbonylations are achieved in solution at room temperature with potassium and cesium diarylamide catalysts. 1 is obtained in excellent yields directly from triethylammonium formate, which may be the product of CO scrubbing with NEt and catalytic hydrogenation.

Trapping of soluble, KCl-stabilized Cu(I) hydrides with CO gives crystalline formates.

Cu(I)-Hydrido complexes supported by dibenzo[]azepinyl -alkene hybrid ligands and stabilized by electrostatic interactions in a Cu-H⋯KCl⋯BR arrangement can be trapped with CO at low temperature to afford Cu(I)-formates. The complexes are isolable with and without a pendant BEt group and show strong Cu-O and weak B-O interactions.