Reaction of (Me3SiNSN)2S with palladium complexes; crystal structures of [PPh4]2[Pd2Br4(S3N2)] and [PPh4][PdBr2(S2N3)]

Reaction of Me3SiNSNSNSNSiMe3 with [PPh4]2[Pd2Cl6] resulted in a mixture of [PPh4][PdCl2(S2N3)] and [PPh4]2[Pd2Cl4(S3N2)]; in addition to the analogous bromo species, reaction with [PPh4]2[Pd2Br6] also generated [PPh4]2[Pd2Br6(S2N2)]. The crystal structure of [PPh4][PdBr2(S2N3)], only the second full characterization of a complex of [S2N3]–, confirmed the presence of two distinct S–N bond lengths (1.49 and 1.6 Å), while the 15N NMR spectrum of partially 15N-labelled [PPh4][PdCl2(S2N3)] confirms the absence of protonation on the S–N ligand. Potential mechanisms for these reactions are discussed.