Show simple item record

dc.contributor.advisorMason, W. Royen_US
dc.contributor.authorChastain, Steven K.en_US
dc.date.accessioned2018-10-05T18:38:35Z
dc.date.available2018-10-05T18:38:35Z
dc.date.issued1981
dc.identifier.urihttps://commons.lib.niu.edu/handle/10843/19113
dc.descriptionIncludes bibliographical references.en_US
dc.descriptionIncludes illustrations.en_US
dc.description.abstractElectronic absorption and magnetic circular dichroisn (MCD) spectral measurements are reported for the octahedral nd⁶ carbonyl and cyano complexes M(CO)₆ (M = Cr, Mo, W) and K₄[M(CN)₆] (M = Fe, Ru, Os), the linear nd¹⁰ complexes [M(CNC₂H₅)₂]ClO₄ (M = Ag, Au, Hg), [Au(P(OR)₃)₂]ClO₄ (R = CH₃, C₂H₅), [Au(CNCH₃)CN], and the tetrahedral 3d¹⁰ complexes K₃[Cu(CN)₄], and [Cu(CNC₂H₅)₄]ClO₄. The intense absorptions observed for the M(CO)₆ and [M(CN)₆]⁴⁻ complexes are characterized as metal to ligand charge transfer (MLCT) from the occupied metal d orbitals to the empty π* ligand orbitals (t[sub 2g] → t[sub lu]* and t[sub 2u]*). The spectral pattern observed in the MCD for the two lowest allowed bands of the M(CO)₆ is similar and consists of a positive B̲ term for the band near 3.5 μm⁻¹ and a negative B̲ term for the band near 4.4 μm⁻¹. The difference between the MCD for the lowest energy MLCT between M(CO)₆ and [M(CN)₆]⁴⁻ complexes is discussed in terms of relative p orbital participation in the empty t[sub lu]* ligand orbital. The rich absorption and MCD spectra for [Au(CNC₂H₅)₂]C1O₄ are interpreted in terms of MLCT excitations (d(σ⁺[sub g], δ [sub g], π[sub g]) → π*). A detailed interpretation of [Au(CNC₂H₅)₂]C1O₄ spectra is given based on an energy level scheme which includes spin-orbit coupling. Spectral assignments for [Au(CNC₂H₅)₂]⁺ are compared to the similar absorption bands in the [Au(CN)₂]⁻, [Au(P(OR)₃)₂]⁺, and [Au(CNCH₃)CN] complexes. The results are also discussed in terms of d orbital participation in bonding with these π- acceptor ligands. The spectra for K₃[Cu(CN)₄] consists of two major absorption bands at 4.21 and 4.85 μm⁻¹. The MCD for these bands show two distinct positive A̲ terms for both absorption bands. These bands are assigned to a MLCT and ligand to ligand (π → π*) excitation, respectively. A comparison of these assignments with the spectra of [Cu(CNC₂H₅)₄]ClO₄ is also presented.en_US
dc.format.extentvi, 85 pagesen_US
dc.language.isoengen_US
dc.publisherNorthern Illinois Universityen_US
dc.rightsNIU theses are protected by copyright. They may be viewed from Huskie Commons for any purpose, but reproduction or distribution in any format is prohibited without the written permission of the authors.en_US
dc.subject.lcshDichroismen_US
dc.subject.lcshMetal ionsen_US
dc.subject.lcshLigandsen_US
dc.subject.lcshTransition metal compounds--Magnetic propertiesen_US
dc.titleMagnetic circular dichroism of metal to ligand charge transfer spectra of some selected d⁶ and d¹⁰ transition metal complexesen_US
dc.type.genreDissertation/Thesisen_US
dc.typeTexten_US
dc.contributor.departmentDepartment of Chemistryen_US
dc.description.degreeM.S. (Master of Science)en_US


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record