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We find that CO ligates selectively to nitrogen tetra-coordinated Co(i) single metal atom sites at room temperature in a manganese–cobalt bi-metallic coordination network self-assembled on graphene. The bound state is metastable, determined by pressure-dependent equilibrium conditions between adsorption and desorption, with an upright, end-on bonding geometry (binding energy 0.73 eV). The ligand v
