The complexes [ReO(SRf)3(PPh3)] and [ReN(SRf)2(PPh3)2] [Rf = C6F5 (1) and (6), C6F4-4-H (2) and (7), C6H4-2-F (3) and (8), C6H4-3-F (4) and (9) and C6H4-4-F (5) and (10)] were synthesized in good yields by reacting [ReOCl3(PPh3)2] or [ReNCl2(PPh3)2] and the lead salt of the corresponding fluorobenzenethiol [Pb(SRf)2]. In contrast, when the free thiol HSC6F5 was employed in the presence of NEt3 as base, the ionic species [ReO(SC6F5)4][NEt3·HCl] (11) was isolated. The X-ray crystal structure of 3 was determined. © 2001 Elsevier Science B.V.