Interactions and 2D NOESY. Pd(II) and Pt(II) cylometallation chemistry

Phase sensitive, 1 H 2D NOESY measurements have been made on a variety of N,N ′‐dimethylbenzylamine cyclopalladated complexes with coordinated ligands having pendant CH moieties. For 8‐methylquinoline and benzo [ h ] quinoline it can be shown that the quinoline‐methyl and benzoquinoline CH‐10 moieties, respectively, reside in a pseudo fifth coordination position above the square planar complex. This information arises primarily from NOEs from one NCH 3 and H3′, the proton ortho to the PdC bond. Similar NOESY studies have also been carried out for (i) a cyclopalladated aliphatic analog based on Pd(NO 3 (L){N(CH 3 ) 2 CH 2 C (CH 3 )(OCH 3 )CH 2 } and (ii) a cyclopalladated phosphite (C∩oP), of the form Pd(NO 3 )(L){P(OEt) 2 OC 6 H 4 }. New platinum complexes of the type trans ‐[PtCl 2 L (tertiary phosphine or tertiary arsine)] are presented, and the spin–spin coupling constants from the pendant CH of L to the 195 Pt are discussed. Several of these complexes can exist in two geometric forms, i.e., for the phosphite complexes: P trans to N, C trans to O as against P trans to O, C trans to N. A distinction between these isomers is made using the same 1 H NOESY spectra that provide information concerned with the pendant CH functions.