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Title: Synthetic, spectroscopic and structural studies on carbametallaboranes containing aromatic and fused aromatic ring systems
Author: Lewis, Zoe G.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1991
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Chapter 1 gives an overview of carbaborane chemistry, including concepts of cluster bonding and slip distortions in carbametallaboranes derived from [7,8-nido-C2B9H11]2-. This is followed by an introduction to the transition metal chemistry of fused aromatic ligands, with specific reference to the similar bonding capabilities of these and carborane species. Finally, the structure of 3-(η5-C9H7)-3,1,2-closo-C2B9H11 (1) is discussed with rationalisation of the observed cisoid molecular conformation. Chapter 2 comprises two sections, A and B. Section A presents the syntheses and structures of three indenyl carbametallaboranes, 1-Ph-3-(η5-C9H7)-3,1,2-closoC2B9H10 (2), 1-(CH2OCH3)-3-(η5-C9H7)-3,1,2-closo-C2B9H10 (3) and 1,2-(CH2OCH3)2-3-(η5-C9H7)-3,1,2-closo-C2B9H9 (4). In 2 and 3 the indenyl ligand adopts a conformation analogous to that in 1, i.e. the indenyl ring junction carbon atoms are cisoid with respect to the cage carbon atoms. In 4 the presence of two ether substituents has resulted in the adoption of the 'next best' staggered conformation. A series of EHMO calculations performed on idealized models of 1-4 predict theoretical energy minimum conformations in broad agreement with those observed crystallographically. Section B describes the synthesis and structural determination of the first reported fluorenyl carbametallaborane complex, 3-(η5-C13H9)-3,1,2-closo-C2B9H11 (5). The molecular conformation has been rationalised in terms of the trans influence of the facial cage boron atoms, and is in full accord with that predicted by the results of EHMO calculations on an idealised model of 5.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available