Redox properties of C6S8(n-) and C3S5(n-) (n = 0, 1, 2): stable radicals and unusual structural properties for C-S-S-C bonds.
The new anionic carbon sulfides C6S10(2-) and C12S16(2-) are described and crystallographically characterized. The C12S16(2-) anion consists of two C6S8 units connected by an exceptionally long (2.157(12) A) S-S bond. In solution, C12S16(2-) exists in equilibrium with the radical C6S8(-*). The equilibrium constant for radical formation (293 K, THF) is 1.2 x 10(-4) M, as determined by optical spectroscopy at varying concentrations. Radical formation occurs through scission of the S-S bond. On the basis of variable temperature EPR spectra, the thermodynamic parameters of this process are DeltaH = +51.5 +/- 0.5 kJ x mol(-1) and DeltaS = +110 +/- 3 J x mol(-1) x K(-1). C6S10(2-) is an oxidation product of C3S5(2-) and consists of two C3S5 units connected by an S-S bond. The S-S bond length (2.135(4) A) is long, and the CS-SC torsion angle is unusually acute (52.1 degrees ), which is attributed to an attractive interaction between C3S2 rings. The oxidation of (Me4N)2C3S5 occurs at -0.90 V vs Fc+/Fc in MeCN, being further oxidized at -0.22 V. The similarity of the cyclic voltammogram of (Me4N)2C6S10 to that of (Me4N)2C3S5 indicates that C6S10(2-) is the initial oxidation product of C3S5(2-).
School of Chemical Sciences and the Frederick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
J G
JG
Breitzer
A I
AI
Smirnov
L F
LF
Szczepura
S R
SR
Wilson
T B
TB
Rauchfuss
D017554:Carbon Compounds, Inorganic / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013440:Sulfides / Q000138:chemical synthesis / Q000737:chemistry*
D017554:Carbon Compounds, Inorganic; D013440:Sulfides; C092035:carbon sulfide