Syntheses, spectroscopic and solid state characterizations of 2,6-bis(diazasilaphosphetidineamino)pyridine 7 and 2,6-bis(di-tert-butylphosphineamino)pyridine 8, and their group 6 and group 10 metal complexes are described. The PNP pincer ligands 7 and 8 were synthesized in good yields by dilithiation of 2,6-diaminopyridine and further treatment with P-chloro-diazasilaphosphetidine and di-tert-butylchlorophosphine, respectively. For the electronic investigations of ligands 7 and 8, their metal carbonyl complexes were synthesized. The syntheses of {2,6-[(tBu)2PNH]2C5NH3W(CO)3} (10), {2,6-[Me2Si(tBuN)2PNH]2C5NH3Mo(CO)3}(11), {2,6-[Me2Si(tBuN)2PNH]2C5NH3Cr(CO )3}(12) and {(2,6-[Me2Si(tBuN)2PNH]2C5NH3)2W(CO)3} (13), were achieved by treatment of ligands 7 and 8 with M(CO)3(CH3CN)3. The electronic properties of these metal carbonyl complexes were studied by IR and 13C NMR. The syntheses of {2,6-[Me2Si(tBuN)2PNH]2C5NH3NiBr2} (14) and {2,6-[Me2Si(tBuN)2PNH]2C5NH3NiBr [BF4]} (15) were accomplished by treating ligand 7 with [NiBr2(CH3OCH2CH2)2O] and AgBF4. These nickel complexes may be used as precatalysts in olefin polymerization processes.