Silver(i) complexes of N-thiophosphorylated bis(iminophosphorane) ligands: From monomers to polymers

Abstract

Treatment of diphosphines Ph₂P(CH₂)_nPPh₂ (n = 1, 2, 4, 6) and [Fe(η⁵-C₅H₄PR′₂)₂] (R′ = Ph, ⁱPr) with a two-fold excess of (RO)₂P(S)N₃ (R = Et, Ph) results in the high-yield formation of the N-thiophosphorylated bis(iminophosphorane) derivatives (CH₂)_n[P{NP(S)(OR)₂}Ph₂]₂ and Fe(η⁵-C₅H₄[P{NP(S)(OR)₂}R′₂])₂, respectively. The reactions of these ligands with AgSbF₆ in a 1 : 1 molar ratio have been investigated. The resulting silver(I) complexes, derived from the selective coordination of the PS units, have been characterized by IR, NMR and MS (FAB) spectroscopy and, in selected cases, by X-ray crystallography. Monomeric, dimeric and polymeric solid-state structures, depending on the nature of the ligand backbone, have been found.