These authors contributed equally.
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†
Article first published online: 11 DEC 2013
Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 53, Issue 4, pages 1103–1108, January 20, 2014
How to Cite
Nova, A., Suh, H.-W., Schmeier, T. J., Guard, L. M., Eisenstein, O., Hazari, N. and Maseras, F. (2014), 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. Angew. Chem. Int. Ed., 53: 1103–1108. doi: 10.1002/anie.201307618
We acknowledge support from the National Science Foundation through Grant CHE-1150826, the Research Council of Norway through a Centre of Excellence Grant (Grant No. 179568V30), the ICIQ Foundation, the Spanish MINECO (projects CTQ2011-27033, Consolider Ingenio 2010 CSD2006-0003), and the French CNRS and Ministère de l’Enseignement Supérieur et de la Recherche.
- Issue published online: 21 JAN 2014
- Article first published online: 11 DEC 2013
- Manuscript Revised: 11 NOV 2013
- Manuscript Received: 29 AUG 2013
- National Science Foundation. Grant Number: CHE-1150826
- Research Council of Norway. Grant Number: 179568V30
- ICIQ Foundation
- Spanish MINECO
- French CNRS
- Ministère de l’Enseignement Supérieur et de la Recherche
- electronic structure;
- four-center two-electron bonds;
- hypervalent silicon;
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.