Mehmet, Nilgun; (1995) Synthetic and structural studies on dinuclear rhodium (ii) compounds. Doctoral thesis (Ph.D), UCL (University College London).

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Abstract

This thesis describes synthetic and structural studies on dinuclear rhodium(II) compounds. The emphasis is on derivatives in which only two ligands bridge the Rh-Rh bond. The removal of one of the axial pyridine molecules from the compound [Rh2(O2CCH3)2(CF3COCHCOCF3)2(NC5H5)2] is described in chapter two. The resulting compound [Rh2(O2CCH3)2(CF3COCHCOCF3)2(NC5H5)] has been structurally characterized using 1H NMR and 19F NMR spectroscopy, and X-ray crystallography. The X-ray diffraction study reveals a coupling between two adjacent molecules via Rh-O(acetate) interactions in the unit cell. The removal of the remaining pyridine molecule is also described. Chapter three describes the preparation of the novel compounds [Rh2(O2CCH3)2(l,10-phen)2Cl2] and [Rh2(HNOCCF3)2(l,10-phen)2Cl2] and their corresponding dicationic pyridine adducts, which have been fully characterised using 1H NMR spectroscopy. The crystal structures of the pyridine adducts [Rh2(O2CCH3)2(l,10-phen)2(NC5H5)2]-[PF6]2 and [Rh2(HNOCCF3)2(l,10-phen)2(NC5H5)2][PF6]2 are reported. Attempts to remove the axial pyridine molecules using a variety of methods are described. The reactions of 2-phenylpyridine (Hppy) and 6-pheny1-2,2'-bipyridine (Hpbipy) with [Rh2(O2CCH3)4] are described in chapter four. Cyclometallation was attempted using the ligands as their mercury salts, [Hg(ppy)C1] and [Hg(pbipy)C1]. The structures of the axial adducts [Rh2(O2CCH3)4(Hppy)2] and [Rh2(O2CCH3)4(Hbipy)2] are reported. An interesting cyclometallated monomer [Rh(O2CCH3)(ppy)2] which is formed in acetic acid is described and its crystal structure reported. Chapter five describes the preparation and crystal structure determination of the compounds [Rh2(dmg)4(NC5H5)2], and [Rh2(O2CCH3)2(dmg)2(EPh3)2] (E = P, As, Sb). The results of electrochemical studies on these compounds is also reported.

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