Migratory insertion and hydrogenation of a bridging azide in a thiolate-bridged dicobalt reaction platform

A novel well-defined thiolate-bridged dicobalt azido complex is converted to a rare sulfilimide-bridged dicobalt complex via nitrogen atom migratory insertion into the Co–S bond upon thermolysis. Intriguingly, the homolytic cleavage of hydrogen is achieved by this azide under mild conditions to furnish a partially hydrogenated azido complex.