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Title: 1,1ʹ-Bis(ortho-carborane) : ruthenium chelates, phosphines and tether derivatives
Author: Riley, Laura E.
ISNI:       0000 0004 7969 7137
Awarding Body: Heriot-Watt University
Current Institution: Heriot-Watt University
Date of Award: 2017
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Chapter one provides a brief exposition on the history and importance of boron and carboranes and introduces 1,1ʹ-bis(o-carborane). It also provides literature examples of 1,1ʹ-bis(o-carborane) chelates, 1,1ʹ-bis(o-carboranyl)phosphines and tethered 1,1ʹ-bis(o carboranes). Chapter two discusses the reaction between dilithiated 1,1ʹ-bis(o-carborane) and di halogenated ruthenium compounds to afford several new compounds of the formula [Ru(κ2/3-2,2ʹ(3ʹ)-{1-(1ʹ-1ʹ,2ʹ-closo-C2B10H10)-1,2-closo-C2B10H10})(L)]. The first compound prepared, whereby L = p-cymene, reacts with either PPh3 or dppe and shows unusual displacement of the p-cymene ligand and a change in the bonding mode of 1,1ʹ bis(o-carborane). The fully saturated (MeCN or CO) derivatives of these compounds are also synthesised and studied, some of which are excellent examples of illustrating the structural trans effect. The initial {Ru(p-cymene)} was tested as a catalyst and displayed good Lewis acid catalytic activity of a Diels-Alder cycloaddition. Chapter three explores two carboranylphosphines [µ-2,2ʹ-PR-{1-(1ʹ-1ʹ,2ʹ-closo C2B10H10)-1,2-closo-C2B10H10}], where R = Et or Ph. Two-dimensional NMR spectroscopy and DFT calculations are used to explain an unusual lack of observed 2JPH coupling in the 1H NMR spectrum of the ethyl derivative. Their subsequent reactions with {AuCl} and {Se} are also discussed as they provide a route to identifying the steric bulk and electronic properties of these carboranylphosphines. Chapter four discusses one new tethered 1,1ʹ-bis(o-carborane) and its comparison with non-carborane analogues. A known tethered carborane is also synthesised and its single decapitation and metalation with {Ru(p-cymene)} explored producing the desired 12 vertex ruthenacarborane/12-vertex carborane but also an unusual 13-vertex diruthenacarborane/12-vertex carborane. Chapter five gives all the synthetic and analytical details for the compounds discussed. Appendix one provides crystallographic tables and appendix two provides all the crystallographic information on a CD. Appendix three includes copies of all published work related to this thesis (to date).
Supervisor: Welch, Alan J. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available