Degree Type

Dissertation

Date of Award

1991

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Robert E. McCarley

Abstract

This research work involves both solid state and solution chemistry. In the area of solid state chemistry, a number of exciting reduced ternary molybdenum oxides containing both discrete oligomeric cluster units (K[subscript]3Mo[subscript]14O[subscript]22 (1) and BaMo[subscript]5O[subscript]8 (2)) and infinite metal-metal bonded chains (KMo[subscript]4O[subscript]6 (3) and Sr[subscript]0.62Mo[subscript]4O[subscript]6 (4)) were discovered. Compound 1 contains discrete oligomeric units of three trans-edge-shared Mo[subscript]6 octahedra interconnected by Mo-O-Mo bonding to form chains along the monoclinic c-axis. The discrete oligomeric cluster units contained in compound 2 (Ba[subscript]2Mo[subscript]10O[subscript]16) are trans-edge-shared Mo[subscript]10 bioctahedral clusters interconnected along the a-axis of the monoclinic cell. The couplings between oligomeric clusters in compounds 1 and 2 are identical and can be described by the general formula Mo[subscript] 4n+2O[subscript] 6n+2O[subscript]4/2, where n is the number of Mo[subscript]6 octahedra trans-edge-fused together. Compounds 3 and 4 are members of this series with the infinite chain of trans-edge-shared Mo[subscript]6 octahedral cluster units. All the compounds reported so far are structurally characterized by (Mo[subscript]4O[subscript]6) octahedral cluster chains which are coupled through Mo-O-Mo interchain linkages to weave a puckered square pattern (except the case of KMo[subscript]4O[subscript]6 where a square pattern is formed) and form channels parallel to the chain axis in which the ternary metal ions are located;In the area of copper(II) alkoxide chemistry, several interesting complexes with the anion of 2-(2-hydroxyethyl)pyridine (hep) as ligands have been synthesized and structurally characterized. Compounds (CuCl(hep)) [subscript]2 (5), (CuCl(hep)(Hhep)) [subscript]2 ·2CH[subscript]2Cl[subscript]2 (6), and (CuCl(hep)(py)) [subscript]2 ·CH[subscript]2Cl[subscript]2 (7) are doubly bridged copper(II) dimers involving a Cu[subscript]2O[subscript]2 moiety. Compound 5 may also be described more accurately as a polymer of dimers. The dimers are linked in a stairstep fashion along (111) through intermolecular Cu-Cl-Cu linkages. Interestingly, compounds 6 and 7 are each interconvertable with 5. When under reduced pressure, 6, and 7 each lose the apical ligand and CH[subscript]2Cl[subscript]2 solvent to form the polymer of dimers 5. Notably, compound 5 has an extremely strong antiferromagnetic coupling (2J = -1298 ± 138 cm[superscript]-1) between two copper(II) centers within the dimer. In the compound (Cu(hep)[subscript]2 ·LiOS[subscript]3CF[subscript]3) [subscript]2 ·4CH[subscript]2Cl[subscript]2 (8), a cis configuration of two hep ligands about the Cu atom is observed. The Cu(hep)[subscript]2 monomers in 8 are held together through two bridging Li[superscript]+ ions of lithium trifluoromethylsulfonate to form a dimer;The partially characterized compounds K[subscript]0.5M[subscript]1.9Mo[subscript]14O[subscript]22 (M = Ca, Sr, Ba, Pb, and Sn), Ca[subscript] 3-xMo[subscript]14O[subscript]22, Sn[subscript]3.6Mo[subscript]16O[subscript]24, PbMo[subscript]6O[subscript]10, and a novel copper(II) alkoxide complex are also reported in this work. ftn*DOE Report IS-T-1510. This work was performed under Contract W-7405-eng-82 with the Department of Energy.

DOI

https://doi.org/10.31274/rtd-180813-11247

Publisher

Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/

Copyright Owner

Sheng-Chang Chen

Language

en

Proquest ID

AAI9126184

File Format

application/pdf

File Size

212 pages

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