| dc.description.abstract | This dissertation consists of two independent topics: (1) a molecular loop with
interstitial channels in a chiral environment; (2) study of formation of metal-metal bonds
in dinickel, dipalladium and dititanium complexes
On the first topic, a study of the reaction products of the interaction of cis-
Mo2(DAniF)2(CH3CN)4
2+ corner pieces with ortho-, meta- and para- isomers of
enatiomerically pure –O2CCH(CH3)C6H4CH(CH3)CO2
– dicarboxylate was performed.
First, an enantiomerically pure molecular loop based on two dimolybdenum units and
two para-dic arboxylate linkers was synthesized and structurally characterized. Similar
reactions with isomeric ortho- and meta- dicarboxylate linkers, as well as with some
nonchiral ligands, showed that the structure of the obtained products depends on the
geometry of the ligand. Meta- dicarboxylate linker favors the formation of the chelated
product and ortho- dicarboxylate linker produces the mixture of chelated molecules and
loops. On the second topic, an investigation of the formation of metal-metal bonds was
performed. Study of the one-electron bond obtained upon oxidation of Ni2
4+ and Pd2
4+ to
Ni2
5+ and Pd2
5+, respectively, was made. The compounds synthesized were studied with
various physical methods, such as X-ray crystallography, UV-visible spectroscopy and
EPR spectroscopy. The nature of oxidized species as well as the dependence of metalmetal
interactions on electron-donating abilities of bridging ligands was studied. It was
shown that oxidation takes place on a metal center. The formation of one-electron bond
in oxidized species is proposed.
Finally formation of Ti2
6+ single bonded compounds by the reduction of two Ti4+
monomers to Ti2
6+ dimer was studied. The nature of the species obtained in solution and
in solid state is discussed. The crystal structure shows the presence of two types of hpp
ligands – chelating and bridging. NMR study of this compound in solution proposes the
rearrangement of this structure to a paddlewheel. | en |
