Welcome to LookChem.com Sign In|Join Free

Article Doi

Structural Isomerism in Silver Thioether Macrocyclic Chemistry: the Synthesis, Redox Properties and Crystal Structures of n(aneS5)n>n, aneS5)2>2 and aneS5)>(B(C6F5)4> (aneS5 = 1,4,7,10,13-pentathiacyclopentadecane)

DOI: 10.1039/DT9930000521

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 521 - 532 (1993)

Update date:2022-08-03

Topics:

Authors:

Blake, Alexander J.Blake, Alexander J.

Collison, DavidCollison, David

Gould, Robert O.Gould, Robert O.

Reid, GillianReid, Gillian

Schroeder, MartinSchroeder, Martin

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/DT9930000521

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 -, BPh4- or B(C6F5)4-> affords the colourless complexes n(<15>aneS5)n>n, aneS5)2>2 and aneS5)> 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, n(<15>aneS5)n>n crystallises in the orthorhombic space group Iba2 with a = 25.713(3), b = 25.749(3), c = 11.6989(19) Angstroem and Z = 16.The two independent infinite chains of cations in the structure are antiparallel.The stereochemistry at AgI is severely distorted octahedral through an 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) Angstroem, with one thioether donor from an adjacent aneS5)>+ fragment asymmetrically bridging two metal centres, Ag(1)-S(1B) 2.742(5) Angstroem.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) Angstroem.The complex aneS5)2>2 crystallises in the triclinic space group P1/ with a = 11.462(3), b = 11.895(3), c = 27.019(10) Angstroem, α = 78.503(18), β = 84.729(13), γ = 67.118(18) deg, and Z = 2.The structure of the 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) Angstroem, 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) Angstroem.Thus, one S-donor of each macrocycle bridges asymmetrically between the two metal centres.The complex aneS5)> crystallises in the triclinic space group P1/ with a = 12.476(5), b = 13.658(7), c = 15.608(6) Angstroem, α = 108.300(22), β = 108.467(17), γ = 100.518(21) deg and Z = 2.The structure contains discrete mononuclear aneS5)>+ cations and - anions.The geometry at AgI is asymmetric wih 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) Angstroem.In MeCN solution aneS5)>+ shows a chemically reversible AgI-AgII redox couple at E1/2 = 0.76 V and a quasi-reversible AgI-Ag0 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.

View More

Products guided by the article

Product name:{Ag(C10H20S5)}(1+)*{B(C6F5)4}(1-)={Ag(C10H20S5)}{B(C6F5)4}

Cas No:148418-38-6

148418-38-6

R&D Labs maybe for 148418-38-6

Relevant to this article

Hot Product