Donor-Stabilized Silyl Cations. 9. Two Dissociation Patterns of Hexacoordinate Silicon Complexes: A Model Nucleophilic Substitution at Pentacoordinate Silicon1

Citations Over TimeTop 1% of 2005 papers

Abstract

Hexacoordinate silicon bischelates with bulky monodentate alkyl ligands tend to ionize, while those with electron-withdrawing CF3 substituents on the chelate rings resist ionization. A hexacoordinate silicon complex with both of these structural features was prepared and was found, by its temperature-dependent 29Si NMR spectroscopy, to undergo a reversible neutral dissociation of the N→Si dative bond, which satisfies both tendencies. The results are supported by crystallographic structure analyses and by nonempirical MO calculations of isodesmic reaction energies.

Related Papers

• → ORGANOSILICON COMPOUNDS CONTAINING A CYANO-GROUP(1962)3 cited
• → Electrochemistry of Organosilicon Compounds(2009)1 cited
• → 3-dinitrobenzoylhydrazones of organosilicon carbonyl compounds(1964)
• → ChemInform Abstract: PREPARATION OF CARBOFUNCTIONAL ORGANOSILICON COMPOUNDS SUBSTITUTED IN THE α‐POSITION. I. ORGANOSILICON THIOLS AND CARBOFUNCTIONAL DERIVATIVES OF SILICON WITH AMINO GROUPS(1977)
• Silicon Organic Compounds. (Book Reviews: Organosilicon Compounds. vol. 1, Chemistry of Organosilicon Compounds; Organosilicon Compounds. vol. 2, parts 1 and 2, Register of Organosilicon Compounds)(1965)