The reaction [Pt3(M3-CO)(ji-dppm)3]2+, 1, with RNC (R = f-Bu, cyclohexyl or o-xylyl) gives an intermediate characterized as [Pt3(ji-CO)(CNR)(/i-dppm)3]2+, 2, which then isomerizes to the stable complex [Pt3(/x3-CO)-(CNR)(ju-dppm)3]2+, 3. When R = o-xylyl, reaction of 3 with more RNC gives an intermediate [Pt3(/i-CO)-(CNR)2(M-dppm)3]2+, 4, which then loses CO to give [Pt3(CNR)2(/i-dppm)3]2+, 5, the first example of a Pt3 cluster complex having no bridging atom. The cluster 5 has been characterized by an X-ray structure determination. [The solvated salt crystallizes in the monoclinic space group P2t, cell dimensions a = 17.639(2) A, b = 19.704(3) A, c = 14.5444(12) A, and /3 = 101.99(2)°w ith Z = 2. Full matrix least-squares refinement on F2 of 558 variables converged at a conventional R factor of 0.0393 for 6334 data with I > 2a(l).] The two xylyl isocyanide ligands are trani-bonded to Pt(l), and as a result the Pt(2)-Pt(3) distance of 2.548(1) A is significantly shorter than the mean of the two distances to Pt(l), 2.649(1) A. Complexes 3 and 5 are fluxional; the RNC ligands can migrate easily around the face of the Pt3 triangle. The diisocyanides 1,4-C^NC6R4N^C, R = H or Me, react with 1 to give polymeric complexes j[Pt3(/u-l,4-C=NC6R4N=C)(/i-dppm)3][PF6]2}?!, 7, in which the diisocyanide bridges between Pt3 cluster units. The local stereochemistry at platinum is similar to that in 5, and the fluxionality appears even easier in 7 than in 5. Evidence is presented for diisocyanide complexes analogous to 2 and 3, namely [Pt3(^t-CO)(CNC6H4NC)(M-dppm)3]2+ and [{Pt3(>i3-CO)(/Li-dppm)3j2(/u-CNC6H4NC)]4+, 8. Calculations of the EHMO type on model complexes give insight into the factors which influence the preferred binding mode (terminal or triply bridging) of the isocyanide at the Pt3 triangle.