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

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), ZnCl₂} networks and a 3-D {AgNO₃} coordination polymer with unprecedented topology. Coordination to the open shell transition metals {NiCl₂, Ni(NO₃)₂, Cu(NO₃)₂, CuBr₂, CuCl₂, CuF₂, CuSO₄} leads to discrete diligand complexes. Protonation of the copper(II) complexes predominantly forms monoligand species, which can aggregate into higher nuclearity clusters. Protonated Cu(NO₃)₂ and CuBr₂ complexes (HNO₃ and HBr, respectively) remain mononuclear. CuCl₂ and CuBr₂ complexes protonated with HCl, however, form trinuclear species comprising trigonal planar μ₃-chloro ligands that aggregate into 1-D trinuclear copper(II) chains via hydrogen-bonded interactions. Protonated CuF₂ forms a tetranuclear cubane type structure that aggregates into a 3-D nanoporous network via hydrogen-bonded interactions. Protonation of the CuSO₄ 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.

Name dc:type.qualificationname

d_ph

Level dc:type.qualificationlevel

d_ph

Grantor dc:publisher.institution

University of Birmingham

Year dc:date.issued

2003

Author dc:creator

• Seeber, Georg Peter Maria

• QD Chemistry

Repository record dc:identifier.uri

http://etheses.bham.ac.uk//id/eprint/95/4/Decl_IS_Seeber03PhD.jpg

OAI identifier oai:identifier

oai:etheses.bham.ac.uk:95