Formation of thiolene versus dithiolene species from TTBEO. Crystal structures of [Au(ddtCO2Et)(PPh3)] and [Sn(ddtCO2Et)2Me2] {TTBEO = 2,5,7,9-tetrathiabicyclo[4.3.0]non-1(6)-en-8-one; ddtCO2Et = 3-(ethoxycarbonylsulfanyl)-5,6-dihydro-1,4-dithiine-2-thiolate}

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Elena Cerrada, J. Felipe García, Mariano Laguna, Raquel Terroba and M. Dolores Villacampa


Abstract

Thiolene gold(I) and tin(IV) complexes such as [Au(ddtCO2R)L] [L = PPh3, PPh2Me or AsPh3; R = Et or Me; ddtCO2R = 3-(alkoxycarbonylsulfanyl)-5,6-dihydro-1,4-dithiine-2-thiolate] and [Sn(ddtCO2R)2Me2] have been obtained from solutions of TTBEO {2,5,7,9-tetrathiabicyclo[4.3.0]non-1(6)-en-8-one} with sodium ethoxide or methoxide and the corresponding halogeno-complexes [AuCl(L)] and SnMe2Cl2. Reaction of the same solutions with [N(PPh3)2]2[ZnCl4] and [ZnCl2(N–N)] [N–N = 1,10=phenanthroline (phen) or 2,2′-bipyridine (bipy)] afforded the dithiolene complexes [N(PPh3)2]2[Zn(dddt)2], [Zn(dddt)(phen)] and [Zn(dddt)(bipy)] which are the transmetallating starting materials for the synthesis of dithiolene gold(I) and tin(IV) complexes [{Au2(dddt)(AsPh3)}n], [Au2(dddt)(PPh3)2], [Au2(dddt)(PPh2Me)2] and [Sn(dddt)Me2]. The results point to the existence of both thiolene ddtCO2R and dithiolene dddt2– species in TTBEO solutions with sodium alkoxide. The crystal structures of [Au(ddtCO2Et)(PPh3)] and [Sn(ddtCO2Et)2Me2] confirm the presence of the ethoxycarbonylsulfanyl ligand.


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