Synthesis, structure and electrochemistry of organometallic compounds bearing C(_n)N ligands

Abstract

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 [(_2)] (M = Ni, Pd, Pt) and [(_2)] (M = Ni, Pd , Pt), which feature a group 10 tetracyanometallate as a bridging moiety.