Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.652780
Title: Studies of transition metal tetraaza macrocyclic complexes
Author: Hyde, T. I.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1987
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Abstract:
A macrocyclic ligand can be regarded as a protecting group for a metal centre, controlling its stereochemical, electronic and redox properties. These properties were examined byulilizing ten 14 membered neutral macrocycles with varying ring substituents and donor groups. A study into the insertion of the platinum metals into four tetraaza 2, 6-pyridyl macrocycles with varying carbon and nitrogen alkylation was instituted. The single crystal X-ray structures of Pd(II), Rh(III), Ru(II) and Ir(III) metal inserted complexes were determined including the species [RuL3(CO)Cl]+ and [IrL4(H)Cl]+ that may be regarded as catalytic intermediates. A comparison of the redox properties of seven Ni(II) and Pd(II) tetraaza macrocycles was studied. Controlled potential electrolysis of [Pd(TMC)]2+, (TMC = 1,4,8,11-tetramethyl 1,4,8,11-tetraazacyclo-tetradecane) at a Pt gauze in acetonitrile afforded a reduction product assigned as a mononuclear Pd(I) complex, [Pd(TMC)]+. The effect of varying one hetero atom donor of a 2,6-diimino pyridyl macrocycle was studied by structural and electrochemical techniques for a series of nickel (II) complexes containing tetraaza, triazaphosphorus and triazathia donor sets. The first reduction product of the triazaphosphorus complex is metal based whereas for the tetraaza complex previous studies had shown the reduction to be ligand based. Reaction of the nickel (I) tetraaza macrocycles (NiL)+, (L = TMC, C rac HMC) with dioxygen in acetonitrile gave the same product as the reaction of [NiL]2+with superoxide ion. With use of isotopic labelling experiments the reactive product was assigned as a nickel (III) - peroxo species, [Ni(III)L(O2)]+.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.652780  DOI: Not available
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