Density functional theory study on the interstitial chemical shifts of main-group-element centered hexazirconium halide clusters; synthetic control of speciation in [(Zr6ZCl12)] (Z = B, C)-based mixed ligand complexes

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dc.contributorHughbanks, Timothy
dc.creatorShen, Jingyi
dc.date.accessioned2005-08-29T14:41:55Z
dc.date.accessioned2017-04-07T19:50:20Z
dc.date.available2005-08-29T14:41:55Z
dc.date.available2017-04-07T19:50:20Z
dc.date.created2003-05
dc.date.issued2005-08-29
dc.description.abstractThe correlation between NMR chemical shifts of interstitial atoms and electronic structures of boron- and carbon-centered hexazirconium halide clusters was investigated by density functional theory (DFT) calculation. The influences of bridging halide and terminal ligand variations on electronic structure were examined respectively. Inverse proportionality was found between the chemical shifts and the calculated energy gaps between two Kohn-Sham orbitals of t1u symmetry, which arose from the bonding and antibonding interaction between the zirconium cage bonding orbitals and the interstitial 2p orbitals. Chemical shielding properties of the interstitial atoms were calculated with Gauge Including Atomic Orbital (GIAO) method. Stepwise ligand substitution of terminal chlorides on [(Zr6CCl12)Cl6]4-cluster by tri(n-butyl)-phosphine oxide (Bu3PO) was conducted with the aid of TlPF6. Composition of the reaction mixtures was analyzed by use of both 13C and 31P NMR. A preliminary scheme for synthesis and separation of [(Zr6CCl12)Cl6-x(Bu3PO)x]x-4 (x = 3 ?? 5) mixture based on solubility difference was reevaluated. Three 1,10-phenanthroline based bidentate ligands, namely, 2,9-Bis(diphenyl-phosphinyl)-1,10-phenanthroline, 2,9-Bis(diethoxyphosphoryl)-1,10-phenanthroline, and 2,9-Bis(di-n-butoxyphosphoryl)-1,10-phenantholine, were synthesized for bridge-chelating the hexazirconium clusters. Coordination chemistry of these ligands with the [Zr6BCl12] and [Zr6CCl12] clusters was subject to preliminary investigation.
dc.identifier.urihttp://hdl.handle.net/1969.1/2444
dc.language.isoen_US
dc.publisherTexas A&M University
dc.subjectDensity Functional Theory
dc.subjectInterstitial Chemical Shifts
dc.subjectHexazirconium Halide Cluster
dc.subjectMixed Ligand Complexes
dc.subjectAxial Ligand Substitution
dc.subjectTri(n-butyl)-Phosphine Oxide
dc.subjectPhenanthroline
dc.subjectChelate
dc.titleDensity functional theory study on the interstitial chemical shifts of main-group-element centered hexazirconium halide clusters; synthetic control of speciation in [(Zr6ZCl12)] (Z = B, C)-based mixed ligand complexes
dc.typeBook
dc.typeThesis

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