Coordination chemistry of cis,trans-1,3,5-Triaminocyclohexane : from mononuclear complexes to supramolecular architectures

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http://eprints.org/relation/isVersionOf http://etheses.bham.ac.uk/id/document/283 http://eprints.org/relation/isVolatileVersionOf http://etheses.bham.ac.uk/id/document/283 http://eprints.org/relation/isIndexCodesVersionOf http://etheses.bham.ac.uk/id/document/283 archive 4031 disk0/00/00/00/95 2008-04-24 10:27:59 2019-01-23 09:51:31 2011-07-19 16:12:55 thesis show 0 Seeber Georg Peter Maria seeber7@gmail.com Cronin Leroy University of Birmingham Coordination chemistry of cis,trans-1,3,5-Triaminocyclohexane : from mononuclear complexes to supramolecular architectures unpub QD 30sch_chem Coordination Chemistry, Inorganic Chemistry, cis,trans-triaminocyclohexane, tach The coordination chemistry of the rigid, aliphatic triamino ligand \(cis,trans\)-1,3,5-triaminocyclohexane (\(trans\)-tach) is investigated. With closed shell transition metals, \(trans\)-tach forms 1-D {Ag(OTf), ZnCl\(_2\)} networks and a 3-D {AgNO\(_3\)} coordination polymer with unprecedented topology. Coordination to the open shell transition metals {NiCl\(_2\), Ni(NO\(_3\))\(_2\), Cu(NO\(_3\))\(_2\), CuBr\(_2\), CuCl\(_2\), CuF\(_2\), CuSO\(_4\)} leads to discrete diligand complexes. Protonation of the copper(II) complexes predominantly forms monoligand species, which can aggregate into higher nuclearity clusters. Protonated Cu(NO\(_3\))\(_2\) and CuBr\(_2\) complexes (HNO\(_3\) and HBr, respectively) remain mononuclear. CuCl\(_2\) and CuBr\(_2\) complexes protonated with HCl, however, form trinuclear species comprising trigonal planar \(\mu_3\)-chloro ligands that aggregate into 1-D trinuclear copper(II) chains via hydrogen-bonded interactions. Protonated CuF\(_2\) forms a tetranuclear cubane type structure that aggregates into a 3-D nanoporous network via hydrogen-bonded interactions. Protonation of the CuSO\(_4\) diligand complex maintains the diligand coordination, forming a 1-D nanoporous network through hydrogen-bonded interactions. Coordination to square planar palladium(II) ions forms all possible coordination motifs (‘Tail’ = monodentate, ‘Head’ = bidentate coordination). ‘Head-to-Head’ coordination results in diligand complexes, ‘Head-to-Tail’ coordination forms cyclic hexanuclear structures and ‘Tail-to-Tail’ coordination leads to a trinuclear species. Extension of \(trans\)-tach via Schiff base formation with pyridine-2-carboxaldehyde results in a hexadonor ligand suitable for metal coordination. Depending on the stoichiometry of the metal, mono- or polynuclear complexes are formed. 2003-12 graduation 2310703 eng author unchecked This unpublished thesis/dissertation is copyright of the author and/or third parties. The intellectual property rights of the author or third parties in respect of this work are as defined by The Copyright Designs and Patents Act 1988 or as modified by any successor legislation. Any use made of information contained in this thesis/dissertation must be in accordance with that legislation and must be properly acknowledged. Further distribution or reproduction in any format is prohibited without the permission of the copyright holder. public 276 University of Birmingham School of Chemistry d_ph na 2003-12 graduation