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EPSRC Reference: GR/K78300/01
Title: NEW DIRECTIONS IN PHOSPHINO & ARSINOALKYNE CHEMISTRY: APPLICATIONS IN ORGANIC SYNTHESIS
Principal Investigator: Doherty, Dr S
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department: School of Chemistry
Organisation: Newcastle University
Scheme: Standard Research (Pre-FEC)
Starts: 01 October 1996 Ends: 30 September 1999 Value (£): 16,396
EPSRC Research Topic Classifications:
Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:
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Summary on Grant Application Form
Phosphinoalkynes exhibit a rich and remarkable chemistry with low valent transition metal complexes, however, their reactivity towards early transition metal reducing fragments has, to date, been neglected. This research initiative seeks to develop the chemistry of the phosphino- and arsinoalkynes Rx E(C=CR)33-x (x-0, 1, 2; E=P, As) towards the reactive gragment Cp2Zr , firstly by considering them as functionalised alkynes (x=2) and then as stabilised diynes and triynes (x-o, 1). We propose to preapre lightly stabilised synthons such as.................. and investigate their selective cross coupling reactions to synthesise a range of cyclic and acyclic main group atom containing compounds. Our studies will be extended to include coupling reactions of bis- and trisalkynylphosphines and arsines with Cp2Zr and Cp2Zr(...2-benzyne). Reactions of the former reagent will most likely generate new flexible macrocycle and/or heterocyclic polymers while new polydentate ligands are expected from the reactions that involve CP2Zr(...2-benzyne). Finally, we will develop a new generation of alternative 2-electron reducing metal fragment by replacing Cp2Zr with the isolobal fragments CpM(NR) (M=Nb,Ta) and M(NR)2 (M-Mo, W). This phase of the programme will involve an evaluation of their potential for mediating organic transormations commonly performed by Negishi's agent. The ability to deploy high levels of expertise in organometallic chemistry together with aspects of organic synthesis constitutes a major factor of this programme.
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Organisation Website: http://www.ncl.ac.uk