Synthesis and characterization of oxorhenium-'3+1' mixed-thiolate complexes. Crystal and molecular structures of [ReO{eta(3)-(SCH2CH2)(2)S}(C6H4X-4-CH2S)] (X = F, Cl, Br, OMe) and of the pendant thiolate compounds [ReO{eta(3)-(SCH2CH2)(2)S}-(eta(1)-SCH2CH2SCH2CH2SH)] and [ReO{eta 3-(SCH2CH2)(2)S}-{eta(1)-SCH2CH(OH)CH(OH)CH2SH}]

The reaction of [(n-C4H9)(4)N][ReOBr4(OPPh3)] with bis(2-mercaptoethyl) sul fide produces [ReOBr{eta(3)-(SCH2CH2)(2)S}] (1), which can be reacted in tu rn to replace the labile bromine atom with various monodentate thiolate lig ands. The reactions of [ReOBr(eta(3)- (SCH2CH2)(2)S}] (1) with (C(6)H(4)X4- CH2S) where X = Br, Cl, F and OMe in alcohol treated with triethylamine has led to the isolation of a series of rhenium complexes of the type [ReO{(SC H2CH2)(2)S}(C6H4X-4-CH2S)]. The reaction of [ReOCl3(DMS) (OPPh3)] with 2-me rcaptoethyl sulfide and base results in the isolation of [ReO{eta(3)-(SCH2C H2)(2)S}(eta(1)-SCH2CH2SCH2CH2SH)] (6) while the reaction of 1 with dithioe rythritol and triethylamine results in the formation of [ReO{eta(3)-(SCH2CH 2)(2)S} {eta(1)-SCH2CH(OH)CH(OH)CH2SH}] (7), unusual examples of '3 + 1' co ordination chemistry with a pendant thiol arm. The X-ray structures of [ReO (eta(3)-(SCH2CH2)(2)S}(C6H4X-4-CH2S)] (X=Br (2), Cl (3), F (4), and OMe (5) ), [ReO(eta(3)-(SCH2(CH2)(2)S){eta(1)-SCH2CH2SCH2CH (6) and [ReO(eta(3)- (S CH2CH2)(2)S}{eta(1)-SCH2CH(OH)CH2CH(OH)CH2SH}] (7) have been determined. (C ) 1999 Elsevier Science S.A. All rights reserved.