Synthesis and reactivity of palladium(I) derivatives with bis(diphenylphosphino)amine. X-ray crystal structure of Pd2(μ-dppa)2Cl2·(CH3)2CO

R. Uson, J. Fornies, R. Navarro, M. Tomas, C. Fortuño, J. I. Cebollada, A. J. Welch

Research output: Contribution to journalArticle

Abstract

ClPd(μ-dppa)2PdCl [dppa = bis(diphenylphosphino)aminel (1) has been prepared by treating PdCl2(NCPh)2 with Pd2(dba)3·.CHCl3 (dba = dibenzylideneacetone) and dppa in CH2Cl2. Substitution reactions allow the synthesis of the neutral BrPd(μ-dppa)2 PdBr (2) and the cationic [Ph3PPd(μ-dppa)2PdPPh 3](BPh4)2 (4) derivatives. Complex 1 reacts with SnCl2 yielding Cl3SnPd(μ-dppa)2PdSnCl3 (3). The species R2N+ and SO2 insert into the PdPd bond of 1 to give the appropriate A-frame PdII-PdII complexes. Extrusion of SO2 takes place at room temperature. CO does not react with 1 in CH2Cl2 at room temperature. The insertion-elimination reactions of 1 with isonitriles RNC (R = p-Tol Cy) have been studied. The molecular structure of ClPd(μ-dppa)2PdCl·(CH3)2CO has been established by a single crystal X-ray study. The crystals are monoclinic, space group P21/c, with a = 13.540(3), b = 16.943(2), c = 21.082(15) Å, β = 105.257(42)° and Z = 4. The final R factor was 0.033 for 5091 observed reflections. The PdPd distance is 2.6378(6) Å.

Original languageEnglish
Pages (from-to)1045-1052
Number of pages8
JournalPolyhedron
Volume8
Issue number8
DOIs
Publication statusPublished - 1989

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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