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Metal–ligand cooperation has proven to be a viable concept for σ bond activation and catalysis, however there are few examples involving phosphorus as an active participant in bond cleavage. The reactivity of E–H bonds (E = S, O) across a metal–phosphorus bond of a cobalt( i ) center ligated by a tridenate N-heterocyclic phosphido (NHP − ) ligand with diphosphine sidearms, (PPP) − , has been explored. Addition of PhOH to (PPP)CoPMe 3 ( 1 ) cleanly affords (PP OPh P)Co(H)PMe 3 ( 2 ), in which the O–H bond was heterolytically cleaved across the M–P NHP bond. Addition of PhSH to 1 first generates (PP H P)Co(SPh)PMe 3 ( 3 ), which undergoes an intermolecular rearrangement to generate (PP SPh P)Co(H)PMe 3 ( 4 ) as the thermodynamic product. A comparison with a related platinum( ii ) system reveals the subtle effects that variations in metal intrinsic properties can have on metal–ligand bifunctional σ bond activation processes.