First paramagnetic PdII complex with a PdN4S 2 coordination core

Safin, Damir [UCL] Babashkina, M.G. [UCL] Garcia, Yann [UCL]

Reaction of the potassium salt of N-thiophosphorylated thiourea 2-PyNHC(S)NHP(S)(OiPr)2 (HL) with PdCl2 in aqueous MeOH leads to the formation of two mononuclear homoleptic complexes [Pd{2-PyNHC(S)NP(S)(OiPr)2-1,5-S,S′}2] ([Pd(L-1,5-S,S′)2]) and [Pd{2-PyNHC(S)NP(S)(OiPr) 2-1,5,7-N,N′,S}2] ([Pd(L-1,5,7-N,N′,S) 2]), while the mechanically induced solid-state reaction of KL and PdCl2 leads to the exclusive formation of [Pd(L-1,5,7-N,N′,S) 2]. The dithiocoordinated desmotrope is square-planar and diamagnetic, while the second desmotrope is unprecedentedly octahedrally configured and paramagnetic. © The Royal Society of Chemistry 2013.