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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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1365-3075
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Silicon rehybridization and molecular rearrangements in hypercoordinate silicon dichelates

Daniel Kost1 / Boris Gostevskii2 / Inna Kalikhman1

1Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel

2A. E. Favorsky Irkutsk Institute of Chemistry, RAS, Irkutsk, Russian Federation

Conference

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

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

Publication History

Published Online:
2009-01-01

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

Citing Articles

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[2]
Peter Politzer, Jane Murray, Goran Janjić, and Snežana Zarić
Crystals, 2014, Volume 4, Number 1, Page 12
[3]
Jane S. Murray, Laura Macaveiu, and Peter Politzer
Journal of Computational Science, 2014, Volume 5, Number 4, Page 590
[4]
Peter Politzer, Jane S. Murray, Pat Lane, and Monica C. Concha
International Journal of Quantum Chemistry, 2009, Volume 109, Number 15, Page 3773
[5]
V V Negrebetsky, S N Tandura, and Yuri I Baukov
Russian Chemical Reviews, 2009, Volume 78, Number 1, Page 21
[6]
Daniel Kost, Boris Gostevskii, and Inna Kalikhman
ChemInform, 2007, Volume 38, Number 46

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