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Title: Alkyne and alkyne-arene complexes of ruthenium
Author: Mallors, Ruth Louise
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1995
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The introduction begins with an out-line of the cluster surface analogy and looks at the importance of studying small organic molecules on clusters to attain a greater understanding of metallic surfaces. The Chapter goes on to look at the activation of alkynes upon coordination to a cluster and assesses the diverse behaviour of alkynes as ligands, some electron counting considerations are considered. Reaction procedures employed in the synthesis of cluster-alkyne complexes are compared highlighting pros and cons of the different routes. The Chapter concludes with a brief synopsis on the cluster [Ru6C(CO)17]. Chapter two is concerned with the synthesis and characterisation of a series alkyne substituted hexaruthenium carbonyl complexes. It is shown that through the utilisation of the oxidative decarbonylation reagent trimethylamine-N-oxide, Me3NO but-2-yne will successively displace carbonyl ligands to yield the complexes [Ru6C(CO)15(m3:h2:h1:h1-Me2C2)], 2, [Ru6C(CO)14(m3:h2:h1:h1:-Me2C2)(m:h2:h2-Me2C2)], 3. [(Ru6C(CO)12(m3h2:h1:h1-Me2C2)3], 5 and [Ru6C(CO)10(Me2C2)4], 6. It is observed that the octahedral array of atoms in complex 2 undergoes a polyhedral rearrangement when reacted to form 3 which exhibits a capped square based pyramid geometry, Complex 3 loses a carbon monoxide ligand to produce [Ru6C(CO)13(Me2C2)2], 4 via chemical and thermal activation. Complexes 3, 5 and 6 display unusual electron counts of 88 when according to polyhedral electron counting predictions such geometries should have counts of 86, this is discussed. The Chapter goes onto investigate the synthesis of complexes which have difference alkyne ligands bound to the cluster fragment. Complexes [Ru6C(CO)14(Me2C2)(Ph2C2), 7, [Ru6C(CO)15(MeC2Et)], 8, [Ru6C(CO)14(MeC2Et)(Me2C2)], 9 and [Ru6C(CO)12(MeC2Et)(Me2C2)(Ph2C2)], 11 are prepared and characterised. The Chapter closes with concluding remarks and an update of the current state of play of the research.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available