title: Silver(I) Complexes of the Derivatized Crown Thioether Ligands 3,6,9,12,15,18-Hexathianonadecanol and 3,6,9,13,16,19-Hexathiaicosanol. Determination of Stability Constants and the Crystal Structures of [Ag(19-aneS6-OH)][CF(3)SO(3)] and [Ag(20-aneS6-OH)][BF(4)].
abstract: The derivatized 19- and 20-membered macrocyclic thio crowns 3,6,9,12,15,18-hexathianonadecanol C(13)H(26)OS(6) (19-aneS6-OH) (1) and 3,6,9,13,16,19-hexathiacycloicosanol C(14)H(28)OS(6) (20-aneS6-OH) (2) have been synthesized by [1 + 1] cyclization in about 30% yield. The ligands 1 and 2 react readily at room temperature with different silver(I) salts in water and in organic solvents to form in quantitative yields the complexes [Ag(19-aneS6-OH)](+) (3) and [Ag(20-aneS6-OH)](+) (4) for which crystals of X-ray quality were grown by slow diffusion of diethylether into methanol. [Ag(19-aneS6-OH)][CF(3)SO(3)] crystallizes in the triclinic space group P&onemacr; with Z = 2, a = 10.760(1), b = 10.853(2) and c = 11.326(2)Å, and alpha = 78.73(1), beta = 73.47(1), and gamma = 74.99(1) degrees. [Ag(20-aneS6-OH)][BF(4)] also crystallizes in the triclinic space group P&onemacr; with Z = 4. The unit cell constants were determined with a = 10.076(4), b = 10.525(3), and c = 22.135(8)Å, alpha = 93.32(2), beta = 102.43(2), and gamma = 100.32(2) degrees. The complex cations [Ag(19-aneS6-OH)](+) and [Ag(20-aneS6-OH)](+) are coordinated through only four sulfur atoms; thus, a distorted tetrahedral coordination geometry is exhibited. In addition we found a highly asymmetric Ag-S bond lengths distribution throughout all complex cations. The stability constants of [Ag](+) with 1 and 2 and, for comparison with [18-aneS6] (5), have been determined in methanol by potentiometric [Ag](+) measurements. Log K values for the formation of 3, 4, and [Ag(18-aneS6](+) (6) are 12.04 +/- 0.19, 11.49 +/- 0.15, and 12.67 +/- 0.13 respectively. Owing to a comparable macrocyclic effect, the similar log K values are reasonable but, since 6 coordinates octahedrally, not expected. (1)H and (13)C NMR investigations at various temperatures give evidence for fluxional coordinative behavior between all six sulfur atoms in solution. Consequently [Ag(19-aneS6-OH)](+), [Ag(20-aneS6-OH)](+), and [Ag(18-aneS6](+) seem to exhibit principally the same solution structures although the solid structures are very different.
authors.affiliation: Division of Radiopharmacy, Paul Scherrer Insitute, CH-5232 Villigen, Switzerland, Institute of Inorganic Chemistry, University of Basel, CH-4056 Basel, Switzerland, AC-Laboratory, AC-Zentrum, CH-3700 Spiez/Switzerland, and Institute of Inorganic Chemistry, University of Tübingen, D-72076 Tübingen, Germany.
authors.forename: Roger
authors.initials: R
authors.lastname: Alberto
authors.forename: Walter
authors.initials: W
authors.lastname: Nef
authors.forename: Alan
authors.initials: A
authors.lastname: Smith
authors.forename: Thomas A.
authors.initials: TA
authors.lastname: Kaden
authors.forename: Markus
authors.initials: M
authors.lastname: Neuburger
authors.forename: Margareta
authors.initials: M
authors.lastname: Zehnder
authors.forename: Alfred
authors.initials: A
authors.lastname: Frey
authors.forename: Ulrich
authors.initials: U
authors.lastname: Abram
authors.forename: P. August
authors.initials: PA
authors.lastname: Schubiger