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Title: Studies of the chemistry of phosphaalkynes and transition metal (I) amidinate and guanadinate complexes
Author: Schulten, Christian
Awarding Body: Cardiff University
Current Institution: Cardiff University
Date of Award: 2009
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Abstract:
The work presented in this thesis is split into two chapters. The first chapter involves the studies of the chemistry of phosphaalkynes and the second chapter involves the preparation and reactivity of transition metal(I) guanidinate and amidinate complexes. The introduction to the first chapter gives general information about the cycloaddition, co-ordination as well as oligomerisation chemistry of phosphaalkynes, and the preparation of the urihindered methyl-phosphaalkyne via a modified literature preparation. Part 1.3.1 shows the reaction of P=CMe and its bulkier analogue P=CBul with 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene and 1,3,5,7-tetraphosphabarrelene, giving differing cycloaddition and oligomerisation products. Part 1.3.2 discusses the reaction of P=CMe with diazomethane, TMS- and 1-adamantyl-azide. Cycloaddition products were isolated and similarities with their bulkier and less bulkier phosphaalkyne analogues were highlighted and discussed. Part 1.3.3 describes the reaction of PCMe with R2E=ER2 (E = Ge or Sn, R = -CH(SiMe3)2) and Ar2Sn=SnAr2 (Ar = C6H2Pri3-2,4,6), showing co-ordination and cycloaddition products in which a 1,3-hydrogen migration has taken place. Differences to the products from their bulkier phosphaalkyne analogues were observed and discussed. Part 1.3.4 describes the reaction of Cp2Ti(NNPri2)(py) with PssCBu1, giving the first cycloaddition product of any transition metal hydrazide complex. Part 1.3.5 describes the cycloaddition reaction of W(CO)5(THF) with PCMe and its bulkier phosphaalkyne analogues. Differences between head to tail and head to head cycloadditions are highlighted and discussed. Part 1.3.6 shows a rare phosphaalkyne V-co-ordination complex formed by reacting P=CMe with MH(dppe)2 (M = Ru or Fe). The results have been compared to those from bulkier phosphaalkynes. Part 1.3.7 shows the reductive coupling reaction of a samarium(II) complex with P=CBu*. The resulting product was compared to similar products from reactions with alkynes and nitriles. Part 1.3.8 shows the co-ordination and cycloaddition reactions of P=CMe with Pt(PCy3)2(r 2-C2H4) and Pt(P-P)(Ti2-C2H4) (P-P = dppe or (PEt3)2). Different products have been observed and the results were compared with those from reactions with bulkier phosphaalkynes.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.584553  DOI: Not available
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