PtCl2 reacts with C6F5CN to give trans-[PtCl2(NCC6F5)(2)] (1) which, in turn, reacts with carbonyl-stabilized phosphorus ylides Ph(3)P=CHR [R = C(O)Me, CO(2)Et] to give trans-[PtCl2{NH=C(C6F5)C(=PPh(3))CO(2)Et}{NCC6F5}] (2a), trans-[PtCl2{NH=C(C6F5)C(=PPh(3))CO(2)Et}(2)] (3a), trans-[PtCl2{E-NH=C(C6F5)C(=PPh(3))C(O)Me}(2)] (3b) or trans-[PtCl2{E-N(=PPh(3))C(C6F5)=CHCO(2)Et}{E-NH=C(C6F5)C(=PPh(3))CO(2)Et}] (4), depending on the reaction conditions. Similarly, Ph(3)P=CHCO(2)Me reacts with trans-[PtCl2(NCMe)(2)] to give trans-[PtCl2{NH=CMeC(=PPh(3))CO(2)Me}(NCMe)] (2b), Complex 3b . CH2Cl2 crystallizes in the triclinic system, space group P (1) over bar, with a = 7.596(2) Angstrom, b = 12.694(3) Angstrom, c = 16.962(3) Angstrom, alpha = 104.28(3)degrees, beta = 102.73(3)degrees, gamma = 104.43(3)degrees, V = 1464.2(6) Angstrom(3), and Z = 1. The structure was refined to values of R1 = 0.0411 and wR2 = 0.1172 [I > 2 sigma(I)] and shows two chloro and two N-bonded beta-imino phosphorus ylide ligands in a trans geometry. Complex 4 crystallizes in the monoclinic system, space group P2(1)/c, with a = 16.400(8) Angstrom, b = 14.354(7) Angstrom, c = 23.221(12) Angstrom, alpha = 90(3)degrees, beta = 92.42(2)degrees, gamma = 90 degrees, V = 5462(5) Angstrom(3), and Z = 4. The structure was refined to values of R1 = 0.0246 and wR2 = 0.0557 [I > 2 sigma(I)]. This complex has also a trans-geometry and shows that while the attack of the ylide on one of the nitrile ligands produces a beta-imino-phosphorus ylide ligand the addition on the second nitrile leads lu an iminophosphorane ligand.