I. Synthesis and characterisation of new main group heteronaphthalenic cations. II. An investigation of the triphenylphosphine chalcogenide-trichloroaluminium(III) adduct systems.
Date
1990
Authors
Royan, Bruce William.
Journal Title
Journal ISSN
Volume Title
Publisher
Dalhousie University
Abstract
Description
In part I of the thesis, the preparation and characterisation of a series of heteronaphthalenic cations, 1*, are described. 1 contain previously unreported $p\pi$-bonding between sulphur and the heavier elements of Group 15 (P, As, Sb). The cations are stabilised by a combination of positive charge, a weakly nucleophilic counter ion and a Hueckel, 10$\pi$-electron count. The thermodynamic stability of 1 is demonstrated by the near planar structures of the halothiazapnictoles, 2g(Cl),g(Br),h. Attempts to prepare non-aromatic derivatives of 1 have resulted in the isolation of novel heterocyclic dications, 21, 24.
Part II of the thesis contains a comprehensive spectroscopic and structural study of the Lewis acid-base adducts, Ph$\sb3$PCh.AlCl$\sb3$ (Ch = O, S, Se). Ph$\sb3$PO.AlCl$\sb3$ exhibits a unique linear backbone both in solution and in the solid state. However, Ph$\sb3$PS/Se.AlCl$\sb3$ are severely bent at the chalcogen centre. The contrasting modes of acid coordination are rationalised in terms of the different contributions of $\pi$- and o-components to the bonding schemes of the free bases. ftn*Please refer to dissertation for diagrams.
Thesis (Ph.D.)--Dalhousie University (Canada), 1990.
Part II of the thesis contains a comprehensive spectroscopic and structural study of the Lewis acid-base adducts, Ph$\sb3$PCh.AlCl$\sb3$ (Ch = O, S, Se). Ph$\sb3$PO.AlCl$\sb3$ exhibits a unique linear backbone both in solution and in the solid state. However, Ph$\sb3$PS/Se.AlCl$\sb3$ are severely bent at the chalcogen centre. The contrasting modes of acid coordination are rationalised in terms of the different contributions of $\pi$- and o-components to the bonding schemes of the free bases. ftn*Please refer to dissertation for diagrams.
Thesis (Ph.D.)--Dalhousie University (Canada), 1990.
Keywords
Chemistry, Organic., Chemistry, Physical.