6-(Diphenylphosphino)-2, 2′-bipyridine (PNN) coordinates to rhenium carbonyls in both κ1 (P) and κ2 (N, N) modes; in the former, the free bpy moiety readily binds to zinc alkyls and halides.[Re (κ1 (P)-PNN)(CO) 5][OTf] reacts with dialkylzinc reagents to form [Re (κ1 (P)- PNN· ZnR)(CO) 4 (μ2-C (O) R)][OTf](R= Me, Et, Bn), in which an alkyl group has been transferred to a carbonyl carbon and the resulting monoalkyl Zn is bound both to the bpy ...