~1HNMR Spectra of Ternary Platinum(II) Complexes with N-Ethyl-or N-Benzyl-1,2-ethanediamine and 2,2'-Bipyridine or 1,10-Phenanthroline:Intramolecular Aroatic-Aromatic Interaction in Coordination Sphere,and It's Solvent and Temperature Effects

摘要

Square-planar complexes with the formaula [Pt(L_1)(L_2)]X_2,where L_1 is di(ammine) or 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) and L_2 is N-ethyl-1,2-ethanediamine (Eten) or N-benzyl-1,2-ethanediamine (Been),and X=NO~3~- or Cl~-,were prepared,NMR measurements of D_2O solutions of these complexes showed that the N-ethyl and N-benzyl groups are forced to take a pseudo axial disposition due to an intramolecular repulsion from hydrogen atoms of aromatic diamines for complexes where L_1=bpy or phen and significant upfield shifts due to the ring current effect were observed for the Been complexes.An analysis of coupling with N-H and ~(195)Pt showed that the major rotamer due to rotation around CH_2-NH is (-)-syn for the Been with a significant intramolecular stacking between aromatic rings of L_1 and L_2,but anti-for the Eten complexes.The solvent and temperature dependency of the upfield shift of the Been complexes are described;the protein denaturatnts,guanidinium chloride,and urea,act to reduce stacking as dioxane.