An unusual example of hypervalent silicon: A five-coordinate silyl group bridging two palladium or nickel centers through a nonsymmetrical four-center two-electron bond

Ainara Nova, Hee Won Suh, Timothy J. Schmeier, Louise M. Guard, Odile Eisenstein, Nilay Hazari, Feliu Maseras

Research output: Contribution to journalArticleResearchpeer-review

29 Citations (Scopus)

Abstract

Pd and Ni dimers supported by PSiP ligands in which two hypervalent five-coordinate Si atoms bridge the two metal centers are reported. Crystallographic characterization revealed a rare square-pyramidal geometry at Si and an unusual asymmetric M2Si2 core (M=Pd or Ni). DFT calculations showed that the unusual structure of the core is also found in a model in which the phosphine and Si centers are not part of a pincer group, thus indicating that the observed geometry is not imposed by the PSiP ligand. NBO analysis showed that an asymmetric four-center two-electron (4c-2e) bond stabilizes the hypervalent Si atoms in the M2Si2 core. Strange to the core: In Pd and Ni dimers supported by PSiP ligands in which two hypervalent five-coordinate Si atoms bridge the two metal centers, a rare square-pyramidal geometry at Si and an unusual asymmetric M2Si 2 core were observed. Natural bond orbital analysis showed that an asymmetric four-center two-electron (4c-2e) bond stabilizes the hypervalent Si atoms in the M2Si2 core (see picture). Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Original languageEnglish
Pages (from-to)1103-1108
JournalAngewandte Chemie - International Edition
Volume53
Issue number4
DOIs
Publication statusPublished - 20 Jan 2014

Keywords

  • electronic structure
  • four-center two-electron bonds
  • hypervalent silicon
  • nickel
  • palladium

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