[2 + 3] cycloaddition of the pyrrolin N-oxide (-)O[upper bond 1 start](+)N[double bond, length as m-dash]CHCH(2)CH(2)C[upper bond 1 end]Me(2) with 2-cyanopyridine NC(5)H(4)(2-CN) in the presence of PdCl(2) at room temperature in acetone gives the ketoimine palladium(II) complex cis-[PdCl(2){N(=[upper bond 1 start]CCH(2)CH(2)C(Me)(2)N[upper bond 1 end]H)C(=O)C(5)H(4)N}] containing the (E)-N-(5,5-dimethylpyrrolidin-2-ylidene)picolinamide ligand, in good yield (85%). The reaction of with 3-cyanopyridine NC(5)H(4)(3-CN) or 4-cyanopyridine NC(5)H(4)(4-CN) under the same experimental conditions gives the simple adducts of cyanopyridines trans-[PdCl(2){NC(5)H(4)(3-CN)}(2)] or trans-[PdCl(2){NC(5)H(4)(4-CN)}(2)] , respectively. When the cyanopyridines NC(5)H(3)R(1)R(2) (R(1) = 2-CN, R(2) = H ; R(1) = 3-CN, R(2) = H ; R(1) = 4-CN, R(2) = H ; R(1) = 4-CN, R(2) = 2-Cl ; R(1) = 3-CN, R(2) = 5-Me ) are heated at 100 degrees C for 12 h with 2-butanone oxime (used as a reagent and solvent) in the presence of PdCl(2), the 2,4-dipyridyl-1,3,5-triazapentadienate (or bis-imidoylamidinate) palladium(II) complexes [Pd{HN[double bond, length as m-dash]C(NC(5)H(3)R(2))NC(NC(5)H(3)R(2))[double bond, length as m-dash]NH}(2)] (2-NC(5)H(3), R(2) = H ; 3-NC(5)H(3), R(2) = H ; 4-NC(5)H(3), R(2) = H ; 4-NC(5)H(3), R(2) = 2-Cl ; 3-NC(5)H(3), R(2) = 5-Me ) are synthesized by one-pot template transformations followed by deprotonation by a base (n-PrNH(2)). The compounds were characterized by IR, (1)H and (13)C NMR spectroscopies, FAB(+)-MS, elemental analyses and, in the cases of , , and , also by X-ray diffraction analyses. The catalytic activity of complexes and was studied under microwave irradiation for C-C coupling reactions, in the solid phase on a silica gel support, and it was found that complex is the most active one with the maximum TON of 2.0.10(5) and TOF of 1.3.10(4) min(-1) for Suzuki-Miyaura, and TON of 800 and TOF of 27 min(-1) for Heck reactions.