Crystallographic characterization of the palladium(I) dimers, syn-Pd2Cl2(dppmMe)2 and Pd2Cl2(dppm)2

Gábor Besenyei, László Párkányi, Eszter Gács-Baitz, Brian R. James

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

An X-ray diffraction study on syn-Pd2Cl2(dppmMe)2, syn-1, shows an unusual boat-like conformation of the eight-membered Pd2P4C2 ring. This conformation, containing equatorial Me groups, facilitates access of the Pd-Pd bond to small molecules such as CO, SO2, and elemental sulfur or selenium, and makes the syn isomer more reactive than anti-1. A comparison of bond angles around the Pd and P atoms in the syn- and anti-isomers reveals a more strained geometry of the former, which may also contribute to the stronger propensity of syn-1 to form A-frame adducts. Solution NMR/NOE studies on syn- and anti-1 and their (μ-Se) adducts reveal the structural rigidity of these complexes; the Me groups inhibit the interchange of axial and equatorial positions on the bridging methine C-atom, and solution structures correspond to those in the solid state. The X-ray structure of Pd2Cl2(dppm)2 is, as expected, like that of the corresponding bromo complex; both are analogous to that of anti-1 which adopts a chair conformation within both the fused, five-membered rings.

Original languageEnglish
Pages (from-to)179-187
Number of pages9
JournalInorganica Chimica Acta
Volume327
Issue number1
DOIs
Publication statusPublished - Jan 10 2002

Keywords

  • 1,1-Bis(diphenylphosphino)ethane
  • A-frame complexes
  • Bis(diphenylphosphino)methane
  • Palladium complexes
  • Selenium compounds

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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