Resum
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.
Idioma original | Anglès |
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Pàgines (de-a) | 1103-1108 |
Revista | Angewandte Chemie - International Edition |
Volum | 53 |
Número | 4 |
DOIs | |
Estat de la publicació | Publicada - 20 de gen. 2014 |