Structural Investigations of Palladium(II) and Platinum(II) Complexes of Salicylhydroxamic Acid

Complexes of salicylhydroxamic acid (shaH) with palladium(II) and platinum(II) were investigated. The synthesis of
[Pt(sha)2] was attempted via a number of methods, and ultimately 1H NMR investigations revealed that
salicylhydroxamate would not coordinate to chloro complexes of platinum(II). However, [Pt(sha−H)(PPh3)2] was
successfully synthesized and the crystal structure determined (orthorhombic, space group Pca21 a = 17.9325(19)
Å, b = 11.3102(12) Å, c = 18.2829(19) Å, Z = 4, R = 0.0224). The sha binds via an [O,O] binding mode, in its
hydroximate form. In contrast the palladium complex [Pd(sha)2] was readily synthesized and crystallized as [Pd(sha)2](DMF)4 in the triclinic space group P1̄, a = 7.066(1) Å, b = 9.842(2) Å, c = 12.385(2) Å, α = 99.213(3)°,
β = 90.669(3)°, γ = 109.767(3)°, Z = 1, R = 0.037. The unexpected [N,O‘] binding mode of the salicylhydroxamate
ligand in [Pd(sha)2] prompted investigation of the stability of a number of binding modes of salicylhydroxamic acid
in [M(sha)2] (M = Pd, Pt) by density functional theory, using the B3LYP hybrid functional at the 6-311G* level of
theory. Geometry optimizations were carried out for various binding modes of the ligands and their relative energies
established. It was found that the [N,O‘] mode gave the more stable complex, in accord with experimental
observations. Stabilization of hydroxamate binding to platinum is evidently afforded by soft ligands lying trans to
them.