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Title: The chemistry of osmium and ruthenium diyne clusters
Author: Clarke, L. P.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 1997
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The work describes in this dissertation concerns the syntheses, reactivities and characterisation of some triosmium and tetraruthenium carbonyl clusters with conjugatively unsaturated diynes. While the alkyne chemistry of osmium and ruthenium carbonyl clusters has been explored extensively over the past 20 years, the analogous chemistry of diynes has been less thoroughly explored. Chapter 1 gives a general introduction to the area of carbonyl clusters and their alkyne derivatives in chapter 1, with an emphasis on the group 8 transition metals. Recent and related diyne work is also discussed. The addition reactions of a series of related diyne ligands to the hydridocarbonyl cluster, H2Os3(CO)10, are presented in Chapter 2. This results in hydrogenation of ligands containing simple aliphatic terminal groups. Cluster derivatives from diynes with terminal cyclic aromatic systems have been shown to undergo novel cyclisation reactions resulting in the formation of cluster coordinated fused ring systems. Their subsequent reactivities have been investigated and are the results presented herein. Chapter 3 describes the chemistry of Os3(CO)10(NCMe)2 with 1,3-diyne ligands. The utilisation of ligands with sterically undemanding terminal groups leads to the generation of a number of products exhibiting carbon-carbon bond formation, cyclisations and cluster linkage. Reactions with increasingly sterically demanding diyne ligands are more selective. The substitution chemistry associated with the above products has been investigated. Chapter 4 continues the study of diyne ligands with the hydridoruthenium cluster, H4Ru4(CO)12, leading to a range of tri- and tetraruthenium derivatives exhibiting novel coordination modes, unusual metal core geometries, ligand transformation and varying degrees of ligand hydrogenation. Chapter 5 is concerned with the reactions of Os3(CO)10(NCMe)2 with an alternative series of diyne ligands, in which the alkyne moieties are separated by an arene spacer group. Molecules in which one or both of the alkyne moieties coordinate a triosmium-decacarbonyl unit have been isolated.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available