A series of palladium thiolate complexes of the [Pd(Ph2PC6H4-2-(CH2NMe2))(SRF)(2)] type have been synthesized in good yields by metathetical reactions of [Pd(Ph2PC6H4-2-(CH2NMe2))Cl-2] (1) with [Pb(SRF)(2)], (SRF = -SC6F5, -SC6F4-H, -SC6H4-2-CF3, -SC6H4-4-F, -SC6H4-2-F) and their crystal structures determined. Heck coupling reactions were carried out using [Pd(PhPC6H4-2-(CH2NMe2))(SRF)2], SRF = -SC6F5(2), -SC6F4-4-H(3), -SC6H4-2-CF3 (4), -SC6H4-4-F (5), -SC6H4-2-F (6) complexes as catalysts in order to examine the effect of the thiolates in the reaction of bromobenzene and styrene. The results obtained indicate that the less electron-withdrawing substituents on the thiolate moiety may favor higher yields in the Pd catalyzed Heck reaction using [Pd(Ph2PC6H4-2-(CH2NMe2))(SRF)(2)] as catalysts. (c) 2005 Elsevier B.V. All rights reserved.