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Pure and Applied Chemistry

The Scientific Journal of IUPAC

Ed. by Burrows, Hugh / Weir, Ron / Stohner, Jürgen

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Silicon rehybridization and molecular rearrangements in hypercoordinate silicon dichelates

Daniel Kost
  • Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel
/ Boris Gostevskii
  • A. E. Favorsky Irkutsk Institute of Chemistry, RAS, Irkutsk, Russian Federation
/ Inna Kalikhman
  • Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel
Published Online: 2009-01-01 | DOI: https://doi.org/10.1351/pac200779061125

Hydrazide-based hypercoordinate silicon dichelates are remarkably flexible in terms of geometry and reactivity: this paper demonstrates how rather subtle constitutional changes result in dramatic geometrical and reactivity changes. A change of ligand-donor group from NMe2 to N=CMe2 changes the solid-state geometry from bicapped tetrahedral to octahedral. These two geometries are shown to coexist in solution in dynamic equilibrium. Hexacoordinate complexes are shown to dissociate to pentacoordinate compounds in two distinct ways: ionic or neutral, depending on substitution. Hexacoordinate dichelates with imino-donor groups undergo a skeletal rearrangement (intramolecular aldol-type condensation of imines), catalyzed by their dissociated halide counterions. However, even in the absence of counterions, silacyclobutane dichelates undergo a similar rearrangement.

Keywords: bicapped-tetrahedral; hexacoordinate; molecular rearrangement; pentacoordinate; rehybridization; silicon


IUPAC International Conference on Physical Organic Chemistry (ICPOC-18), International Conference on Physical Organic Chemistry, ICPOC, Physical Organic Chemistry, 18th, Warsaw, Poland, 2006-08-20–2006-08-25

Published Online: 2009-01-01

Published in Print: 2007-01-01

Citation Information: Pure and Applied Chemistry. Volume 79, Issue 6, Pages 1125–1134, ISSN (Online) 1365-3075, ISSN (Print) 0033-4545, DOI: https://doi.org/10.1351/pac200779061125, January 2009

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