Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.641401
Title: Synthesis and structural studies of polynuclear copper complexes
Author: Baxter, Christopher W.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2004
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Abstract:
This thesis investigates the effect of varying the ligand component in a cluster forming reaction recently developed for the synthesis of molecules with general formula, [Cux+y(C≡CR)x(hfac)y] where hfac is 1,1,1,5,5,5-hexafluoropentanedione and C≡CR is a straight chain terminal alkynyl ligand (R = -C3H7, -C4H9, -C5H11­, - C6H13). Using the ‘bulky’ alkynyl ligands, 3,3-dimethyl-1-butyne (tBuC≡CH) and trimethylsilylacetylene (Me3SiC≡CH) has led to the successful isolation of five clusters containing ten or twelve copper atoms. These molecules are structurally related to a family with formula, [Cu4(aryl)4] and display an alkynyl bridged Cu4 central core ‘capped’ by peripheral Cu-hfac chelate rings. Six additional clusters are reported that have nuclearities ranging between sixteen and twenty-six copper atoms. These were obtained by replacing hfacH with the trifluorinated 1,3-diketonyl ligands, 4,4,4-trifluoro-1-phenyl-1,3-butanedione, (Ph-tfacH), 4,4,4-trifluoro-1-phenyl-1,3-butanedione (tBu-tfacH) and 1,1,1-trifluoro-2,4-pentanedione (tfacH) or using 3,3-dimethyl-1-butyne (tBuC≡CH) or 3-phenyl-1-propyne (PhCH2C≡CH) in the cluster forming reaction. The new additions to the [Cux+y(C≡CR)x(hfac)y] family of molecules are diverse in nuclearity and display interesting structural features. Using alkynyl or 1,3-diketone ligands with bulky substituents affects the ability of the clusters to adopt a ‘conventional’ structure and as a result interesting structural variations are observed. Using ligands with substituents that are able to form weak but significant π-stacking type intramolecular interactions also causes a distortion from a ‘conventional’ structure. There is an interesting common structural motif that appears throughout the [Cux+y(C≡CR)x(hfac)] family. This motif has the formula, [Cu4(C≡CR)4(Cu-hfac)x] and all the clusters in the series are found to contain one, two or three such fragments.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.641401  DOI: Not available
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