Bisarylated complexes trans‐[Pd(Fmes)2(SR2)2] [Fmes = 2,4,6‐tris(trifluoromethyl)phenyl (fluoromesityl); SR2 = SMe2, tht; tht = tetrahydrothiophene] are precursors for various bisarylated fluoromesityl palladium(II) complexes by ligand‐substitution reactions. Boiling under reflux in acetonitrile gives the mixed complexes trans‐[Pd(Fmes)2(NCMe)(SR2)], whereas boiling under reflux in toluene leads to trans‐[PdCl2L2] (L = PMe3, tBuNC, pTol‐NC, 4‐MePy), in the presence of neutral monodentate ligands, or to (NnBu4)[trans‐Pd(Fmes)2I(SR2)] when treated with (NnBu4)I. trans‐[Pd(Fmes)2(SMe2)2] reacts with bidentate ligands, also boiling under reflux in toluene, to give [Pd(Fmes)2(L−L)] [L−L = Me2bipy, 2,2′‐biquinolyl, κ2N,N′‐OCPy2, dppm (Ph2PCH2PPh2), dppe (Ph2PCH2CH2PPh2), pte (PhSCH2CH2SPh), κ2S,N‐SPPh2Py, κ2O,N‐OPPhPy2], or the bimetallic complex [Pd(Fmes)2(μ‐1κN:1,2κO:2κN‐Py2MeCO)Pd(Fmes)(SMe2)] (characterized by X‐ray diffractometry) when treated with (OH)(CH3)CPy2. The crowding associated with two Fmes groups produces several interesting features: (1) trans complexes are preferred over cis complexes, against the expected electronic preferences; (2) the low‐temperature NMR spectra of several complexes, or the X‐ray diffraction structure of [Pd(Fmes)2(2,2′‐biquinolyl)], reveal significant structural distortions associated with steric crowding; (3) the need for boiling under reflux in the synthesis suggests a dissociative substitution mechanism, which is unknown so far for Pd; (4) some of the complexes show 19F−19F through‐space couplings. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)