Palladium Goes First: A Neutral Asymmetric Heteroditopic N,P Ligand Forming Pd-3d Heterobimetallic Complexes

A facile two-step synthesis of bis(1-methylhydrazinyl)pyrimidine from pyridine-2-carbaldehyde and 2-diphenylphosphanylbenzaldehyde gave access to the new asymmetric ligand 1. The phosphane selectively guides Pd^II into the softer tridentate N,N,P pocket, yielding monometallic complex 2. A second reaction with a 3d transition metal complex precursor (groups 7 to 12) fills the vacant N,N,N pocket and thus provides a variety of heterobimetallic complexes of the type Pd^II/M^II (M = Mn (3), Fe (4), Co (5), Ni (6), Cu (7), Zn (8)). Single-crystal X-ray diffraction studies were performed for all complexes. The assembly of μ₂-chlorido-bridged dimers was observed for complexes 5-7 in the solid state, while DOSY NMR experiments have shown that 5-7 are unbridged monomers in solution. As an exception, Fe^II prefers to form the homoleptic meridional complex [Fe{PdCl(1)}₂](OTf)₄ (4). The electrochemical behavior and the effective magnetic moment in solution were investigated for all complexes by cyclic voltammetry and Evans method, respectively. Experimental UV/vis results were interpreted by performing TD-DFT calculations on 1, 2, and 3.