Models for Cooperative Catalysis: Oxidative Addition Reactions of Dimethylplatinum(II) Complexes with Ligands Having Both NH and OH Functionality

[Image: see text] The role of NH and OH groups in the oxidative addition reactions of the complexes [PtMe(2)(κ(2)-N,N′-L)], L = 2-C(5)H(4)NCH(2)NH-x-C(6)H(4)OH [3, x = 2, L = L1; 4, x = 3, L = L2; 5, x = 4, L = L3], has been investigated. Complex 3 is the most reactive. It reacts with CH(2)Cl(2) to give a mixture of isomers of [PtMe(2)(CH(2)Cl)(κ(3)-N,N′,O-(L1-H)], 6, and decomposes in acetone to give [PtMe(3)(κ(3)-N,N′,O-(L1-H)], 7, both of which contain the fac tridentate deprotonated ligand. Complex 3 reacts with MeI to give complex 7, whereas 4 and 5 react to give [PtIMe(3)(κ(2)-N,N′-L2))], 8, or [PtIMe(3)(κ(2)-N,N′-L3)], 9, respectively. Each complex 3, 4, or 5 reacts with either dioxygen or hydrogen peroxide to give the corresponding complex [Pt(OH)(2)Me(2)(κ(2)-N,N′-L)], 10, L = L1; 11, L = L2; 12, L = L3. The ligand L3 in complexes 9 and 12 is easily oxidized to the corresponding imine ligand 2-C(5)H(4)NCH=N-4-C(6)H(4)OH, L4, in forming the complexes [PtIMe(3)(κ(2)-N,N′-L4)], 13, and [Pt(OH)(2)Me(2)(κ(2)-N,N′-L4)], 14, respectively. The NH and OH groups play a significant role in supramolecular polymer or sheet structures of the complexes, formed through intermolecular hydrogen bonding, and these structures indicate how either intramolecular or intermolecular hydrogen bonding may assist some oxidative addition reactions.