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Durham e-Theses
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Electrochemical and structural studies of organometallic acetylide complexes

Roberts, Rachel Louise (2005) Electrochemical and structural studies of organometallic acetylide complexes. Doctoral thesis, Durham University.



This thesis describes the synthesis and properties of systems of the general type ML(_x)-bridge- ML(_x), and related 'mixed-valence' derivatives. The efficacy of the l.l'-ferrocenediyl unit (Fc') as a bridge between two redox-active metal centres, is investigated by examination of the properties of a series of complexes, 1,1'-{Cp'(PP)RuC=C}(_2)Fc’, and the related binuclear model systems Ru(C=CFc)(PP)Cp'. Whilst interactions through an ethyndiyl bridge occur between one Ru(PP)Cp' moiety and a ferrocenyl centre, in the l,l'-{Cp'(PP)RuC=C}(_2)Fc' systems no interaction between the terminal Ru(PP)Cp' groups is observed. A comparative study of the redox and spectroscopic properties of the family of complexes [{Ru}(_2)(u-C≡CXC≡C)](^n+) [{Ru} = Ru(PPh(_3))(_2) Cp, Ru(dppe)Cp*; X = 1,4- C(_6)H(_4), l,4-C(_10)H(_6), 9,10-C(_14)H(_8); n = 0, 1, 2] is presented, together with those of the related mononuclear compounds. Comparison of the results with DFT calculations of the electronic structure allows the properties of the diethynylaryl-bridged, bimetallic complexes to be rationalised in terms of a significant contribution of the diethynylaryl bridging ligand to the SOMO. The electronic properties of the 1,12-diethynyl carborane-bridged species 1,12- {Ru(dppe)Cp*}(_2)(u-C≡C-CB(_10)H(_10)C-C≡C), and the related mononuclear complex Ru(C≡C-CB(_10)H(_10)H)(dppe)Cp*, are assessed by a combination of electrochemical and spectroscopic techniques. The results allow a comparison of the 'three-dimensional' aromatic spacer l,12-C(_2)BH(_10) with the phenylene analogue. Explorations of the acetylide chemistry of the Fe(dppe)’_n’ fragment are described. The resulting air stable complexes provide a convenient entry point to the acetylide chemistry of the octahedral iron fragment. The details of additional crystal structures obtained by single crystal X-ray diffraction methods, together with a brief description of the chemistry associated with them, are presented in the appendix.

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Thesis Date:2005
Copyright:Copyright of this thesis is held by the author
Deposited On:08 Sep 2011 18:27

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