Issue 39, 2009

1H NMR spectroscopic identification of binding modes of 2,2′-bipyridineligands in complexes of square-planar d8 metal ions

Abstract

The reaction of [M(bpy)]2+ (M = PdII and/or PtII; bpy = 2,2′-bipyridine) moieties with model nucleobases leads to a variety of products, viz. 1 : 1, 1 : 2 and 2 : 2 (head–tail, ht, or head–head, hh) complexes. By carefully analysing the H5 (H5′) resonances of the bpy ligands, which in all cases occur furthest upfield, and with additional indicators (concentration dependence of H6, H6′ resonances; 195Pt–1H coupling constants, if observable; absolute shifts of H5, H5′), it is possible to assign binding situations of bpy ligands, even in multinuclear complexes with several [M(bpy)]2+ entities in different environments present. The analysis presented here is carried out on X-ray structurally established cases of [M(bpy)]2+ complexes, including three new ones, [Pt(1-MeC-N3)2(bpy)](NO3)2·2.5H2O (5), ht-[(bpy)Pd(N3–1-MeC-N4)2Pd(bpy)](ClO4)2·3H2O (16) and ht-[(bpy)Pd(N1-ampy-N2)2Pd(bpy)](NO3)2·3H2O (17). The data provide a consistent picture, useful for the future assignment of similar bpy complexes in the absence of X-ray structural evidence.

Graphical abstract: 1H NMR spectroscopic identification of binding modes of 2,2′-bipyridine ligands in complexes of square-planar d8 metal ions

Supplementary files

Article information

Article type
Paper
Submitted
02 Mar 2009
Accepted
07 Jul 2009
First published
10 Aug 2009

Dalton Trans., 2009, 8203-8214

1H NMR spectroscopic identification of binding modes of 2,2′-bipyridine ligands in complexes of square-planar d8 metal ions

W. Shen, G. Trötscher-Kaus and B. Lippert, Dalton Trans., 2009, 8203 DOI: 10.1039/B904173G

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