The syntheses of [XPd(μ-dppm)2Pd(C6Cl5)](X = Cl, C6Cl5 are described. Other neutral halogeno-pseudohalogeno-palladium(I) complexes [XPd(μ-dppm)2Pd(C6Cl5)] (X = Br, I, SCN or CNO) have been obtained from [ClPd(μ-dppm)2Pd(C6Cl5)] by metathetical reactions, and SnCl2 inserts into the PdCl bond to give the Pd-SnCl3 compound. The cationic derivatives [LPd(μ-dppm)2Pd(C6Cl5)]BPh4 (L = PPh3, P(OPh)3, AsPh3, SbPh3, tht) have also been prepared. SO2 or RN2+ insert into the PdPd bond of [ClPd(μ-dppm)2Pd(C6Cl5)] to give A-frame PdII complexes, but do not react with (C6Cl5)Pd(μ-dppm)2Pd(C6)Cl5. The nature of the products of the reactions of 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 P1, 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) Å, α 90.49(3), β 89.204(25), γ 102,86(3)°, V 3554.8 Å3. 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 D2d. The PdPd bond length is 2.6704(21) Å.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry