SYNTHESES AND REACTIVITY OF PENTACHLOROPHENYLPALLADIUM(I) DERIVATIVES. MOLECULAR STRUCTURE OF Pd2(μ-dppm)2(C6Cl5)2

Article abstract of DOI:10.1016/S0022-328X(00)99349-5

The syntheses of (X = Cl, C6Cl5) are described.Other neutral halogeno-pseudohalogeno-palladium(I) complexes (X = Br, I, SCN or CNO have been obtained from by metathetical reactions, and SnCl2 inserts into the Pd-Cl bond to give the Pd-SnCl3 compound.The cationic derivatives BPh4 (L = PPh3, P(OPh)3, AsPh3, SbPh3, tht) have also been prepared.SO2 or Rn2(1+) insert into the Pd-Pd bond of to give A - frame Pd(II) complexes, but do not react with (C6Cl5)Pd(μ-dppm)2Pd(C6Cl5).The nature of the products of the reactions XPd(μ-dppm)2Pd(C6Cl5) with RNC (R = t-Bu, Cy, p-Tol, CNC6H4NC) depend on the isonitrile used and the reaction conditions.The molecular structure of (C6Cl5)Pd(μ-dppm)2Pd(C6Cl5) has been established by a single crystal X-ray study.The crystals are triclinic, space group P<*>, with 2 molecules of the 2 CH2ClCH2Cl solvate in a cell of dimensions a 12.986(4), b 13.213(5), c 21.254(6) Angstroem, α 90.49(3), β 89.204(25), γ 102.86(3) degree, V 3554.8 Angstroem³.Of 9156 data collected on a four-circle diffractometer, 4474 observed reflections were used in the refinement (R = 0.0902).The complex has no crystallographically imposed symmetry, but overall is close to D_2d.The Pd-Pd bond length is 2.6704(21) Angstroem.