Synthesis of the first chalcogen-centered diselenophosphinato Zn(II) clusters, [Zn4(μ4-X){Se2PR2}6] (X = S or Se), and a zigzag polymer {ZnBr(μ-Se2PR2)[PyNO]}n

• Self-assembly of the first S- and Se-centered tetranuclear Zn4 cluster with diselenophosphinate ligands.
• Synthesis of zigzag-shaped polymer containing {ZnBr(μ-Se2PR2)[PyNO]} repeating units.
• Structural study of the above coordination compounds.

N,N-Diethylammonium diselenophosphinate, [Et2NH2][Se2PR2] (R = CH2CH2Ph), under mild conditions (r.t., CH2Cl2) reacts with ZnBr2 to afford discrete tetranuclear cluster [Zn4(μ4-Se){Se2PR2}6] in 63% yield, which consists of Se-centered distorted Zn4 tetrahedron ligated by six edge-bridged diselenophosphinato anions (μ2, μ2). In the presence of Na2S2O3 as a S2− source, this reaction provides structurally similar S-centered cluster, [Zn4(μ4-S){Se2PR2}6], in 76% yield. Finally, at the interaction of the N,N-diethylammonium diselenophosphinate with ZnBr2 and pyridine N-oxide (the reagent ratio is stoichiometric), the zigzag polymer {ZnBr(μ-Se2PR2)[PyNO]}n, bearing a “SeZnSeP” repeating chain, was formed in 84% yield.

The discrete tetranuclear S- and Se-centered clusters, [Zn4(μ4-X){Se2PR2}6] (X = S or Se), and diselenophosphinato ZnII zigzag-shaped polymer, {ZnBr(μ-Se2PR2)[PyNO]}n, have been synthesized based on the reaction of ZnBr2 with ammonium diselenophosphinate, [Et2NH2][Se2PR2] (R = CH2CH2Ph).Figure optionsDownload as PowerPoint slide