Effects of the Intramolecular NH···S Hydrogen Bond in Mononuclear Platinum(II) and Palladium(II) Complexes with 2,2‘-Bipyridine and Benzenethiol Derivatives

A series of complexes, [M(bpy)(SAr)2] (M = platinum(II) or palladium(II), bpy = 2,2‘-bipyridine, SAr = 2- or
4-(acylamino)benzenethiolate, or 2-(alkylcarbamoyl)benzenethiolate), were synthesized and characterized on the
basis of 1H NMR, IR, and electrochemical properties. The structures of [Pt(bpy)(S-2-Ph3CCONHC6H4)2] (1) and
[Pt(bpy)(S-2-t-BuNHCOC6H4)2] (3) were determined by X-ray analysis. The complexes have intramolecular NH···S
hydrogen bonds between the amide NH group and the sulfur atom. A weak NH···S hydrogen bond in these
complexes and [Pd(bpy)(S-2-Ph3CCONHC6H4)2] (4) is detected from the 1H NMR spectra and the IR spectra in
chloroform and in the solid state. [Pt(bpy)(S-2-Ph3CCONHC6H4)2] (1) exhibits a remarkably high-energy-shifted
lowest-energy band in UV−visible spectra and has a positively shifted oxidation potential. The blue-shift of 42 nm
and the positive shift of +0.24 V, as compared to those of [Pt(bpy)(SC6H5)2], are due to the effect of the NH···S
hydrogen bond.