Herstellung von 1,2,4-Trithiolan-, 1,2,4,5-Tetrathian- sowie 1,2,3,5,6-Pentathiepan-S-oxiden und deren Reaktionen mit (Ph3P)2Pt(η2-C2H4). Kristallstrukturanalyse von 3,3,5,5-Tetraphenyl-1,2,4-trithiolan-1-oxid

Abstract

Bei der Oxidation von 3,3,5,5‐Tetraphenyl‐1,2,4‐trithiolan (1) mit m‐Chlorperbenzoesäure entsteht selektiv das 3,3,5,5‐Tetraphenyl‐1,2,4‐trithiolan‐1‐oxid (2). Die Molekülstruktur von 2 wurde durch Röntgenstrukturanalyse bestimmt. Die Oxidation von Octamethyltetrathiadispiro[3.2.3.2]dodecan‐2,9‐dion (3) mit Trifluorperessigsäure bei –50 °C liefert das 5‐Oxid 4. Das Octamethylpentathiadispiro[3.3.3.2]tridecan‐2,9‐dion (5) wird mit m‐Chlorperbenzoesäure bei 0 °C zum 12‐Oxid 6 oxidiert. Das 1‐Oxid 2 reagiert mit zwei Äquivalenten (Ph3P)2Pt(η2‐C2H4) (7) zu einem 1 : 1 Gemisch von (Ph3P)2PtSCPh2S (8) und (Ph3P)2Pt(η2‐Ph2C=S=O) (9).

Reaction of 3,3,5,5‐Tetraphenyl‐1,2,4‐trithiolane with Pt0(bisphosphane)(η2‐nbe) Complexes Bearing Bridged Bisphosphane Ligands with Various Bite Angles

“…For both complexes the arrangement of the ligands around the platinum center is distorted square planar. The nonequivalent Pt–P bond lengths in 7b and 7c can be explained by the different trans influence of the sulfur and the carbon atom, respectively, as reported for similar structures 5b,7a,8b. The side‐on coordination of 2 to the Pt 0 (bisphosphane) moiety is clearly visible.…”

Oxidation of Spirocyclohexyl‐1,2,4‐trithiolane and Complexation Reaction with [Pt(η2‐nb)(PPh3)2]

“…The tendency to form the 4‐ S ‐oxide over the 1‐ S ‐oxide is well known for the unsubstituted 1,2,4‐trithiolane and 3,3,5,5‐tetramethyl‐1,2,4‐trithiolane 7,8. In contrast, for the more bulkily substituted derivatives, such as tetraphenyl13 and 3,5‐di‐ tert ‐butyl‐3,5‐diphenyl derivatives,15 exclusive oxidation at S1 and S2 is observed.…”

“…Over the last years, reactions of cyclic disulfanes, thiosulfinates and thiosulfonates with Pt 0 have been described, which result in dithiolato, sulfenato thiolato, sulfinato thiolato, as well as thiosulfonato Pt II complexes. Except for the latter compound, all the compounds were formed by oxidative addition of Pt 0 complexes to the S–S(O) n moiety ( n = 0–2) 9–13. 1,2,4‐Trithiolanes and their 1‐ S ‐oxides undergo reactions with Pt 0 complexes 9,13…”

“…Except for the latter compound, all the compounds were formed by oxidative addition of Pt 0 complexes to the S–S(O) n moiety ( n = 0–2) 9–13. 1,2,4‐Trithiolanes and their 1‐ S ‐oxides undergo reactions with Pt 0 complexes 9,13…”

Platinum Complexes of Naphthalene‐1,8‐dichalcogen and Related Polyaromatic Hydrocarbon Ligands

“…Bond lengths [ä] and angles [8] for complexes 2, 4, 10, 11, 12 and 13, where E = Se for 2 and E = S for 4, 10, 11, 12 and 13. (4) 168.56 (7) 168.97 (18) 172.61 (19) 158.17 (7) 165.56 ( (1) 110.81 (19) 103.38 (19) 110.28 (14) 103.1(3) 114.7 (7) 111.0 (7) 106.3 (2) 106.77 (14) Pt (1) [27] The X-ray structures of 10, 11 and 12 show that the oxygen atoms of the sulfenato groups in 10 and 12 and one oxygen atom of the sulfinato moieties of 11 and 12 lie approximately within the plane of the naphthalene ring. A similar situation is observed in the S(9) sulfinato group of complex 13, in which O(9) and the naphthalene ring are co-planar, whereas the O(1) and O(2) oxygen atoms of the S(1) sulfinato group lie above and below the naphthalene ring plane, respectively; this may be a consequence of the distortion observed in the ligand (see below).…”