Experimental and quantum-chemical studies of 15N NMR coordination shifts in palladium and platinum chloride complexes with pyridine, 2,2′-bipyridine and 1,10-phenanthroline

A series of Pd and Pt chloride complexes with pyridine (py), 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen), of general formulae trans-/cis-[M(pY)(2)Cl-2], [M(py)(4)]Cl-2, trans-/cis-[M(py)(2)Cl-4], [M(bpy)Cl-2], [M(bPy)Cl-4], [M(phen)Cl-2], [M(phen)Cl-4], where M = Pd, Pt, was studied by H-1, Pt-195, and N-15 NMR. The 90-140 ppm low-frequency N-15 coordination shifts are discussed in terms of such structural features of the complexes as the type of platinide metal, oxidation state, coordination sphere geometry and the type of ligand. The results of quantum-chemical NMR calculations were compared with the experimental N-15 coordination shifts, well reproducing their magnitude and correlation with the molecular structure. Copyright (c) 2005 John Wiley & Sons, Ltd.