Structural isomerism in silver thioether macrocyclic chemistry: the synthesis, redox properties and crystal structures of [Ag n ([15]aneS ₅ ) n ][PF ₆ ] n′ [Ag ₂ ([15]aneS ₅ ) ₂ ][BPh ₄ ] ₂ and [Ag([15]aneS ₅ )][B(C ₆ F ₅ ) ₄ ]([15]aneS ₅ = 1,4,7,10,13-pentathiacyclopentadecane)

Reaction of AgNO3 with 1 molar equivalent of [15]aneS5(1,4,7,10,13-pentathiacyclopentadecane) in refluxing MeOH–water gives a colourless solution. Addition of excess of counter ion [PF6–, BPh4– or B(C6F5)4–] affords the colourless complexes [Agn([15]aneS5)n][PF6]n′[Ag2([15]aneS5)2][BPh4]2 and [Ag([15]aneS5)][B(C6F5)4] respectively in high yield. Single-crystal X-ray structural studies on these systems have revealed different cation stereochemistries as the counter ion is altered. Thus, [Agn([15]aneS5)n][PF6]n crystallises in the orthorhombic space group lba2 with a= 25.713(3), b= 25.749(3), c= 11.6989(19)Å and Z= 16. The two independent infinite chains of cations in the structure are antiparallel. The stereochemistry at Ag1 is severely distorted octahedral through an [S4+ S2] donor set, Ag(1)⋯ S(1) 3.219(5), Ag(1)–S(4) 2.659(5), Ag(1)–S(7) 2.651(6), Ag(1)⋯ S(10) 3.075(7), Ag(1)–S(13) 2.564(6)Å, with one thioether donor from an adjacent [Ag([15]aneS5)]+ fragment asymmetrically bridging two metal centres, Ag(1)–S(1B) 2.742(5)Å. A similar geometry is observed at the second Ag ion, Ag(2)⋯ S(1′) 3.263(5), Ag(2)–S(4′) 2.605(5), Ag(2)⋯ S(7′) 2.964(8), Ag(2)–S(10′) 2.713(7), Ag(2)–S(13′) 2.637(6), Ag(2)–S(1D) 2.714(5)Å. The complex [Ag2([15]aneS5)2][BPh4]2 crystallises in the triclinic space group P with a= 11.462(3), b= 11.895(3), c= 27.019(10)Å, α= 78.503(18), β= 84.729(13), γ= 67.118(18)°, and Z= 2. The structure of the [Ag2([15]aneS5)2]2+ cation shows an unusual binuclear stereochemistry with [4 + 1] thioether donation to one silver(I) centre, Ag(2)–S(7′) 2.558(4), Ag(2)–S(10′) 2.623(5), Ag(2)–S(13′) 2.716(5), Ag(2)–S(1) 2.486(3), Ag(2)⋯ S(1′) 3.131(3)Å, and [3 + 1] thioether donation to the other, Ag(1)–S(7) 2.529(3), Ag(1)–S(10) 2.608(4), Ag(1)–S(1′) 2.537(3), Ag(1)⋯ S(1) 2.907(3)Å. Thus, one S-donor [S(1) and S(1′)] of each macrocycle bridges asymmetrically between the two metal centres. The complex [Ag([15]aneS5)][B(C6F5)4] crystallises in the triclinic space group P with a= 12.476(5), b= 13.658(7), c= 15.608(6)Å, α= 108.300(22), β= 108.467(17), γ= 100.518(21)° and Z= 2. The structure contains discrete mononuclear [Ag([15]aneS5)]+ cations and [B(C6F5)4]– anions. The geometry at Ag1 is asymmetric with all five thioether donors of the macrocycle interacting with the metal centre: Ag–S(1) 2.4712(19), Ag ⋯ S(4) 2.7262(20), Ag–S(7) 2.6847(21), Ag–S(10) 2.5621(19), Ag ⋯ S(13) 2.8813(19)Å. In MeCN solution [Ag([15]aneS5)]+ shows a chemically reversible AgI–AgII redox couple at E½= 0.76 V and a quasi-reversible AgI–Ago couple at –0.37 V vs. ferrocene–ferrocenium. The intensely coloured d9 silver(II) oxidation product has been observed by X- and Q-band ESR spectroscopy and the oxidation of AgI to AgII monitored spectroelectrochemically.