Tetra-2,3-pyrazinoporphyrazines with externally appended pyridine rings. 5. Synthesis, physicochemical and theoretical studies of a novel pentanuclear palladium(II) complex and related mononuclear species

New palladium(II) complexes of the free-base tetrakis2,3-(5,6-di-2-pyridylpyrazino)porphyrazine], Py 8TPyzPzH 2], have been prepared and their physicochemical properties examined. The investigated compounds are the pentanuclear species (PdCl 2) 4Py 8TPyzPzPd], the monopalladated complex Py 8TPyzPzPd], and its corresponding octaiodide salt (2-Mepy) 8TPyzPzPd](I) 8. All three Pd (II) complexes have a common central pyrazinoporphyrazine core and differ only at the periphery of the macrocycle, where the simple dipyridinopyrazine fragments present in Py 8TPyzPzPd] bear four PdCl 2 units coordinated at the pyridine N atoms in the pentanuclear complex, (PdCl 2) 4Py 8TPyzPzPd], or carry pyridine-N(CH 3) (+) moieties in the iodide of the octacation (2-Mepy) 8TPyzPzPd] (8+). The structural features of the pentanuclear complex (PdCl 2) 4Py 8TPyzPzPd], partly supported by X-ray data and solution (1)H NMR spectra of the (CN) 2Py 2PyzPdCl 2] precursor, were elucidated through one- and two-dimensional (1)H NMR spectra in solution and density functional theory (DFT) calculations. Structural information on the monopalladated complex Py 8TPyzPzPd] was also obtained from DFT calculations. It was found that in the complex (PdCl 2) 4Py 8TPyzPzPd] the peripheral PdCl 2 units adopt a py-py coordination mode and the generated N 2PdCl 2 moieties are directed nearly perpendicular to the plane of the pyrazinoporphyrazine ring, strictly recalling the arrangement found for the palladated precursor (CN) 2Py 2PyzPdCl 2]. NMR and DFT results consistently indicate that of the four structural isomers predictable for (PdCl 2) 4Py 8TPyzPzPd], one having all four N 2PdCl 2 moieties pointing on the same side of the macrocyclic framework (i.e., isomer 4:0, plus the 3:1 and the 2:2-cis and 2:2-trans isomers), the 4:0 isomer ( C 4 v symmetry) is the predominant form present. According to cyclic voltammetry and spectroelectrochemical results in pyridine, dimethyl sulfoxide (DMSO), and dimethylformamide (DMF), the monopalladated complex Py 8TPyzPzPd] undergoes four reversible or quasi-reversible one-electron ligand-centered reductions, similar to the behavior also observed for the pentanuclear complex (PdCl 2) 4Py 8TPyzPzPd], which shows an additional reduction peak attributable to the presence of PdCl 2. Owing to the electron-withdrawing properties of the PdCl 2 units, the pentanuclear complex is easier to reduce than the mononuclear complex Py 8TPyzPzPd], some related Py 8TPyzPzM] complexes, and their porphyrin or porphyrazine analogues, so much so that the corresponding monoanion radical is generated at potentials close to 0.0 V vs SCE in DMSO or DMF. In turn, the monoanion of (2-Mepy) 8TPyzPzPd](I) 8 is also extremely easy to generate electrochemically. Indeed, because of the eight positively charged N-CH 3 (+) groups in this complex the first reduction occurs at potentials close to +0.10 V in DMSO or DMF. The redox behavior of the mono- and pentapalladated complexes has been rationalized on the basis of a detailed DFT analysis of their ground-state electronic structure.