A molecular loop with interstitial channels in a chiral environment and study of formation of metal-metal bonds in dinickel, dipalladium and dititanium complexes

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Title: A molecular loop with interstitial channels in a chiral environment and study of formation of metal-metal bonds in dinickel, dipalladium and dititanium complexes
Author: Ibragimov, Sergey
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 .
URI: http : / /hdl .handle .net /1969 .1 /3760
Date: 2006-08-16

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A molecular loop with interstitial channels in a chiral environment and study of formation of metal-metal bonds in dinickel, dipalladium and dititanium complexes. Available electronically from http : / /hdl .handle .net /1969 .1 /3760 .

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