Two phosphinites 2,6-OMe, 4-Me, 1-OPR 2 C 6 H 2 (5a: R=Ph; 5b: R= t Bu) were prepared in good yields. Two methoxy groups are placed on the 2,6 positions of the phosphinites deliberately thereby to avoid a plausible orthometallation process while coordinating toward palladium metal. Further reaction of 5a with PdCl 2 in the ratio of 2:1 and 1:1 gave 5a ligated palladium complexes {(5a)PdCl(μ-Cl)} 2 7a and {(5a) 2 PdCl 2 } 8a, respectively. As revealed from their crystal structures, the former is a dimeric complex with anticipated molecular arrangement; nevertheless, the latter is a monomeric complex with unexpected, energetically unfavorable cis form. By contrast, only dimeric form was observed from the reaction of 5b with PdCl 2 . It is believed that the bulky substituents, t Bu, on 5b prevent the formation of a monomeric complex in cis form. Fair to good efficiencies were observed for the Suzuki–Miyaura cross-coupling reactions employed in situ-prepared 5/Pd(OAc) 2 as the catalytic precursor.