FORMATION OF THIOLENE VERSUS DITHIOLENE SPECIES FROM TTBEO - CRYSTAL-STRUCTURES OF [AU(DDTCO(2)ET)(PPH3)] AND [SN(DDTCO(2)ET)(2)ME-2] (TTBEO = 2,5,7,9-TETRATHIABICYCLO[4.3.0]NON-1(6)-EN-8-ONE - DDTCO(2)ET = ONYLSULFANYL)-5,6-DIHYDRO-1,4-DITHIINE-2-THIOLATE)

Thiolene gold(I) and tin(IV) complexes such as [Au(ddtCO(2)R)L] [L = P Ph3, PPh2Me or AsPh3; R = Et or Me; ddtCO(2)R = onylsulfanyl)-5,6-dihy dro-1,4-dithiine-2-thiolate] and [Sn(ddtCO(2)R)(2)Me-2] have been obta ined 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 halo geno-complexes [AuCl(L)] and SnMe2Cl2. Reaction of the same solutions with [N(PPh3)(2)](2)[ZnCl4] and [ZnCl2(N-N)] [N-N = 1,10=phenanthrolin e (phen) or 2,2'-bipyridine (bipy)] afforded the dithiolene complexes [N(PPh3)(2)](2)[Zn(dddt)(2)], [Zn(dddt)(phen)] and [Zn(dddt)(bipy)] wh ich are the trans-metallating starting materials for the synthesis of dithiolene gold(I) and tin(IV) complexes [{Au-2(dddt)(AsPh3)}(n)]. [Au -2(dddt)(PPh3)(2)], [Au-2(dddt)(PPh2Me)(2)] and [Sn(dddt)Me-2]. The re sults point to the existence of both thiolene ddtCO(2)R(-) and dithiol ene dddt(2-) species in TTBEO solutions with sodium alkoxide. The crys tal structures of [Au(ddtCO(2)Et)(PPh3)] and [Sn(ddtCO(2)Et)(2)Me-2] c onfirm the presence of the ethoxycarbonylsulfanyl ligand.