COMPLEXES WITH A TRIFLUOROPHOSPHINE LIGAND BRIDGING A TRIPALLADIUM TRIANGLE - STRUCTURE OF [PD3(MU(3)-PF(3))(MU(3)-I)(MU-BIS(DIPHENYLPHOSPHINO)METHANE)(3)]I

synthetic and structural work describe the first examples of bridging monophosphine ligands. Treatment of Pd2(mu-dpm)2X2 (1; dpm is bis(diphenylphosphino)methane; X is Cl or I) with excess trifluorophosphine yields brown [Pd3(mu3-PF3)(mu-X)(mu-dpm)3]X and yellow Pd(dpm)X2. Metathesis of [Pd3(mu3-PF3)(mu-Cl)(mu-dpm)3]cl with sodium iodide yields red-brown [Pd3(mu3-PF3)(mu3-I)(mu-dpm)3]I. [Pd3(mu3-PF3)(mu3-I)(mu-dpm)3]I.3CH2Cl2 crystallizes in the monoclinic space group Pn with a = 11.149(2) angstrom, b = 15.635(3) angstrom, c = 22.857(5) angstrom, and beta = 90.17(2)-degrees at 130 K with Z = 2. Refinement of 8454 reflections with (F > 4.sigma(F)) and 500 parameters yielded R = 0.063 and R(w) =0.071. The structure of the cation consists of a nearly equilateral triangle of palladium atoms bridged at the edges by dpm ligands and capped by the triply bridging phosphorus atom of the trinuorophosphine, An iodide ligand is almost symmetrically situated n the opposite face. Studies of the Pd2(mu-dpm)2Cl2/PF3 reaction by variable-temperature (P{H})-P-31-H-1 NMR spectroscopy show that a variety of species are formed in the complex reaction that leads to the eventual formation of [Pd3(mu-PF3)(mu-Cl)(mu-dpm)3]Cl.