In this thesis, the synthesis of the organic cyanoacetylenes NCC≡CC(_6)H(_5) and NCC≡CC(_6)H(_4)-4-NMc(_2) and the metal cyanoacetylides Ru(C≡CC≡N)(PPh(_3))(_2)Cp, Ru(C≡CC≡N)(dppe)Cp* and Fe(C≡CC≡N)(dppe)Cp is presented and their coordination chemistry is explored. The structure and electrochemical behaviour of these novel cyano-carbon complexes is investigated and spectro-electrochemical methods are used to investigate the electronic structure of the cyanoacetylide compounds. In addition, in order to gain a greater understanding of the metal/ligand bonding interaction in these systems, the synthesis, structure and electrochemical behaviour of a series of metal nitriles [Ru(N≡CC(_6)H(_4)X)(PPh(_3))(_2)Cp][PF(_6)] (X = NO(_2), NMe(_2), CN) and [M(N≡CC(_6)H(_4)X)L(_2)Cp'][PF(_6)] (M = Ru, L = PPh(_3), Cp' = Cp; M = Ru, L2 = dppe, Cp' = Cp*; M = Fe, L(_2) = dppe, Cp' = Cp) were investigated, as were the complexes [{Ru(PPh(-3))(_2)Cp}(_2){μ-M(CN)(_4)}] (M = Ni, Pd, Pt) and [{Ru(dppe)Cp*}(_2){ μ - M(CN)(_4)}] (M = Ni, Pd , Pt), which feature a group 10 tetracyanometallate as a bridging moiety.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:551515 |
| Date | January 2005 |
| Creators | Cordiner, Richard L. |
| Publisher | Durham University |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://etheses.dur.ac.uk/3007/ |
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