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On the Reaction of Dithioarsonites, L‐As(SPh) 2 (L = Ar, R), with Octasulfur in the Presence of Triethylamine as an Activator. The Crystal Structure of the Sesquisulfide (2‐O 2 N‐C 6 H 4 ‐As) 2 S 3
Author(s) -
Terzis Aris,
Ioannou Panayiotis V.
Publication year - 2004
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200300321
Subject(s) - triethylamine , monoclinic crystal system , chemistry , sulfur , medicinal chemistry , activator (genetics) , sulfide , crystal structure , hydrogen sulfide , stereochemistry , crystallography , organic chemistry , biochemistry , gene
Octasulfur (elemental sulfur) does not react at room temperature with a variety of As III compounds of the type Ar‐As(SPh) 2 and R‐As(SPh) 2 . However, in the presence of catalytic amounts of triethylamine, which probably acts as an activator of octasulfur, reactions do take place. The products isolated from the aromatic dithioarsonites are not the expected Ar‐As(S)(SPh) 2 but the sulfide, cyclo ‐(PhAsS) 4 , and the sesquisulfides, (ArAs) 2 S 3 , which are the same with those obtained by reduction of arylarsonic acids with hydrogen sulfide. The action of S 8 /Et 3 N on aliphatic dithioarsonites did not give any As V products but gave mixtures of non‐separable oligomeric (RAsS) x . Probable mechanistic routes for these reactions are proposed. The known cyclo ‐(PhAsS) 4 and (PhAs) 2 S 3 and the new (2‐O 2 N‐C 6 H 4 ‐As) 2 S 3 have been structurally characterized: (2‐O 2 N‐C 6 H 4 ‐As) 2 S 3 , monoclinic, C2/c, a = 13.564(9)Å, b = 7.982(6)Å, c = 16.67(1)Å, β = 117.63(2)°, V = 1599(2)Å 3 , Z = 4, wR 2 0.0640. The 1, 4‐diarsa‐2, 3, 5‐trithiacyclopentane ring is puckered and the two As III atoms are pseudo tetrahedral.