Redox–Transmetalation Reactions: Easy Access to Homo- and Heterodimetallic d8,d10 Complexes

The ability of the imine PyCHN–CH2Py (Py = 2-pyridyl, bpi) to behave as a heteroditopic ligand, which is suitable for creating two separate compartments to host metals in different oxidation states, has been developed by studying the reactions of the mixed-valence complexes [(cod)M–Ι(μ-bpi)MΙ(cod)] (M = Rh, Ir) with [M′(Cl)2(PPh3)2] (M′ = Pd, Ni). The results depend on the molar ratio of the reagents used (1:1 or 1:2) to give the heterometallic complexes {d10-M′,d8-M}-[(PPh3)(Cl)M′0(μ-bpi)MΙ(cod)] (Pd,Rh, 4; Pd,Ir, 5; Ni,Rh, 8; Ni,Ir, 9) and the two-electron mixed-valent compounds [(PPh3)(Cl)M′0(μ-bpi)M′ΙΙ(Cl)] (M′ = Ni, 10; Pd, 11), respectively. A redox process occurs in the replacement of the low-valent [(cod)M–I] fragment, whereas the exchange of the [(cod)MI] fragment is redox-neutral. The metal with a d8 configuration in the products exhibits a square-planar geometry coordinated to two (Rh/Ir) or three (Ni/Pd) nitrogen atoms of the bridging bpi ligand. Conversely, the metal with a d10 configuration adopts trigonal–planar geometries, π-bonded to the imine CN bond. The isolated complexes 4/5 and 10/11, along with the hypothetical heterometallic Pd,Ni compound (12), were studied by DFT methods. Additionally, the T-shaped moiety ‘M′ΙΙ(PPh3)(Cl)(η1-CH-N(bpi))’, stabilized by a secondary γ-agostic interaction, and the ‘M′II(Cl)(κ3N-bpi)’ fragment was found to be accessible redoxomers of complexes 10 and 11 by DFT calculations.