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Title: Palladium acylation catalysts and osmium cluster arene complexes
Author: Bryce, Garry Thomas
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1998
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The acyl palladium complex (bpy)Pd(COMe)(I) (bpy = 2,2'-bipyridyl) was synthesised, and reacted with a variety of different alkenes, cyclic alkenes and dienes, and arenes in an attempt to yield the inserted acyl complexes {(bpy)Pd(CxRYCOMe)}. The inserted complexes were the first stage in setting up a catalytic reaction with the Palladium complex acting as a catalyst in the synthesis of an acylated arene. The osmium cluster Os3(CO)10(NCMe)2, was reacted with a series of functionalised arenes of the type C6H4R1R2 (where R1 = H, R2 = F, Cl, Br, CHCH3, C(CH3)CH2 and Me; R1 = R2 = Me, R1 = R2 = C(CH3)CH2) yielding clusters of the type Os3(CO)9H2(C6H2R1R2). The crystallographic and spectroscopic data provides evidence of the different geometric forms that the complexes demonstrate with the different types of ligands. The osmium arene complexes were reacted further using a Friedel-Crafts acylation reaction to acylate the arene ring when it is attached to the cluster. The resultant complexes show a shifting of the IR bands in the IR to higher wavenumbers. The compound Os3(CO)9H2(C2H3F) reacted with 2-butyne yielding the complexes Os3(CO)8(H)(CH2CHCHCH3)(C6H3F) and Os3(CO)8H22-2-butyne)(C6H3F) which were identified crystallographically and spectroscopically. These two complexes show two different bonding modes of the butyne ligand to metal centre.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available