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.
Dalton Transactions
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