(N,Se) and (Se,N,Se) Ligands Based on Carborane and Pyridine Fragments – Reactivity of 2,6‐[(1′‐Me‐1′,2′‐closo‐C2B10H10)SeCH2]2C5H3N towards Copper and Silver

Abstract

Two new closo‐carborane selenolated ligands, 2‐[(1′‐Me‐1′,2′‐closo‐C2B10H10)SeCH2]C5H4N (L1) and 2,6‐[(1′‐Me‐1′,2′‐closo‐C2B10H10)SeCH2]2C5H3N (L2), were prepared by the C–H activation of 1‐Me‐1,2‐C2B10H11 with nBuLi, followed by the insertion of elemental selenium into the C–Li bond and reaction with 2‐(BrCH2)C5H4N or 2,6‐(BrCH2)2C5H3N, respectively. The closo species L1 and L2 were deboronated with CsF to give the nido‐carborane cesium salts Cs[2‐{(1′‐Me‐1′,2′‐nido‐C2B9H9)SeCH2}C5H4N] (1) and Cs2[2,6‐{(1′‐Me‐1′,2′‐nido‐C2B9H9)SeCH2}2C5H3N] (2). The isolation of the complexes [Ag(OTf)(L2)] (3, OTf = triflate), [Ag(PPh3)(L2)][OTf] (4), [Cu(L2)(MeCN)][PF6] (5), and [Cu(L2)2][PF6] (6) indicates the coordination ability of L2 towards these metals. The molecular structures of L1 and L2 were established by single‐crystal X‐ray diffraction. Quantum‐chemical calculations confirmed the molecular geometries and also the presence of C–H···Se intramolecular interactions as well as C–H···H–B and B–H···π intermolecular interactions.