The reaction of [NBu(4)](2)[(C(6)F(5))(2)Pt(μ-PPh(2))(2)Pd(μ-PPh(2))(2)Pt(C(6)F(5))(2)] (1a) with [AgPPh(3)](+) results in the oxidation of two bridging diphenylphosphanides to give the 46e species [(PPh(3))(C(6)F(5))(2)Pt(2)(μ-P(2)Ph(2))Pd(μ-PPh(2))(μ-Ph(2)P(4)-P(3)Ph(2))Pt(1)(C(6)F(5))(2)] (3). Complex 3 displays two tetracoordinated terminal platinum centers and a central Pd atom that is bonded to three P atoms and that completes its coordination sphere by a rather long (3.237 Å) dative Pt(2) → Pd bond. Complex 3 is also obtained when [(R(F))(2)Pt(μ-PPh(2))Pd(μ-PPh(2))(μ-Ph(2)P-PPh(2))Pt(R(F))(2)] (2) is reacted with PPh(3). Analogously, the addition of PPh(2)Et, CO or pyridine to 2 affords the 46e complexes of general formula [(L)(C(6)F(5))(2)Pt(2)(μ-P(2)Ph(2))Pd(μ-PPh(2))(μ-Ph(2)P(4)-P(3)Ph(2))Pt(1)(C(6)F(5))(2)] (L = PPh(2)Et, 4; L = CO, 6; L = pyridine, 7). The geometry around Pt(2) is determined by the bulkiness of L bonded to Pt. Thus, in complexes 3 (L = PPh(3)) and 4 (L = PPh(2)Et), the ligand L occupies the trans position with respect to μ-P(2), and in 6 (L = CO), the ligand L occupies the cis position with respect to μ-P(2). Interestingly, for 7 (L = py), both isomers 7-trans and 7-cis, could be isolated. Although 4 did not react with an excess of PPh(2)Et, the reaction with the less sterically demanding CH(3)CN ligand resulted in the opening of the Pt(2)-P(2)-Pd cycle with formation of the saturated 48e species [(PPh(2)Et)(C(6)F(5))(2)Pt(μ-PPh(2))Pd(MeCN)(μ-PPh(2))(μ-Ph(2)P-PPh(2))Pt(C(6)F(5))(2)] (8). The saturated 48e complex [(CO)(C(6)F(5))(2)Pt(μ-PPh(2))Pd(MeCN)(μ-PPh(2))(μ-Ph(2)P-PPh(2))Pt(C(6)F(5))(2)] (9) was obtained by acetonitrile addition to 6. Beside the hindered rotation of the pentafluorophenyl groups and a flip-flop motion of the Pd-P-Pt(1)-P-P ring observed at low T, a rotation about the Pt(2)-P(2) bond and a P-C oxidative addition/reductive elimination process occur for 3 and 4 at room temperature. A "through-space" (19)F-(31)P spin-spin coupling between an ortho-F and the P(4) is observed for complexes 3 and 4, having the C(6)F(5) groups bonded to Pt(2) in mutually trans position. The XRD structures of complexes 3, 6, 7-trans, 7-cis, 8, and 9 are described.