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

Seeber, Georg Peter Maria (2003)
Ph.D. thesis, University of Birmingham.

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Abstract

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.

Type of Work:Ph.D. thesis.
Supervisor(s):Cronin, Leroy
School/Faculty:Schools (1998 to 2008) > School of Chemical Sciences
Department:Chemistry
Keywords:Coordination Chemistry, Inorganic Chemistry, cis,trans-triaminocyclohexane, tach
Subjects:QD Chemistry
Institution:University of Birmingham
Library Catalogue:Check for printed version of this thesis
ID Code:95
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.
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