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Actinide chalcogenido and chalcogenolate compounds

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Title
Actinide chalcogenido and chalcogenolate compounds
Name (type = personal)
NamePart (type = family)
Ringgold
NamePart (type = given)
Marissa
NamePart (type = date)
1991-
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Marissa Ringgold
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RoleTerm (authority = RULIB)
author
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Brennan
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John G
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John G Brennan
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Advisory Committee
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chair
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Goldman
NamePart (type = given)
Alan S
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Alan S Goldman
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Advisory Committee
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internal member
Name (type = personal)
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Greenblatt
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Martha
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Martha Greenblatt
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Advisory Committee
Role
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internal member
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Clark
NamePart (type = given)
Timothy B
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Timothy B Clark
Affiliation
Advisory Committee
Role
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outside member
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Rutgers University
Role
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degree grantor
Name (type = corporate)
NamePart
School of Graduate Studies
Role
RoleTerm (authority = RULIB)
school
TypeOfResource
Text
Genre (authority = marcgt)
theses
OriginInfo
DateCreated (qualifier = exact)
2019
DateOther (qualifier = exact); (type = degree)
2019-01
CopyrightDate (encoding = w3cdtf)
2019
Place
PlaceTerm (type = code)
xx
Language
LanguageTerm (authority = ISO639-2b); (type = code)
eng
Abstract (type = abstract)
Actinide chemistry, specifically thorium and uranium chalcogenolate and chalcogenido complexes are relatively unexplored. Traditionally in literature they contain sterically hindered environments or are synthesized under aqueous conditions. However, it has been discovered that thorium metal reductively inserts into the E-E bond of REER (R= Ph, C6F5; E = S, Se) to from stable chalcogenolate compounds whose size is determined by the identity of the neutral donor ligand or additional chalcogen in air-free, water-free conditions without the use of large bulky ligands.
Thorium cubanes (py)8Th4(μ3-E′)4(μ2-EPh)4(η-EPh)4 (E, E′ = S, Se) were prepared from ligand-based redox reactions of elemental E′ with Th(EPh)4. Products with all four possible E/E′ combinations (E,E′ = S,S; Se,Se; S,Se; Se,S) were isolated and structurally characterized, ligand exchange reactions were explored, and the heterochalcogen compounds (py)8Th4(μ3-S)4(μ2-SePh)4(η-SePh)4 and (py)8Th4(μ3-Se)4(μ2-SPh)4(η-SPh)4 were heated to deliver solid solutions of ThSxSe2−x. NMR spectroscopy indicated that the structure of (py)8Th4(μ3-Se)4(μ2-SePh)4(η-SePh)4 is static in pyridine solution, with no exchange between bridging and terminal PhE− ligands on the NMR time scale. A computational analysis of 77Se NMR shifts provides insight into the solution structure of both clusters and monomeric chalcogenolates.
Thorium chalcogenolates Th(ER)4 react with 2,2’-bipyridine (bipy) to form complexes with the stoichiometry (bipy)2Th(ER)4 (E = S, Se; R = Ph, C6F5). All four compounds have been isolated and characterized by spectroscopic methods and low-temperature single crystal x-ray diffraction. Two of the products, (bipy)2Th(SC6F5)4 and (bipy)2Th(SeC6F5)4 , crystallize with lattice solvent, (bipy)2Th(SPh)4 crystallizes with no lattice solvent, and the selenolate (bipy)2Th(SePh)4 crystallizes in two phases, with and without lattice solvent. In all four compounds the available volume for coordination bounded by the two bipy ligands is large enough to allow significant conformational flexibility of thiolate or selenolate ligands. 77Se NMR confirms that the structures of the selenolate products are the same in pyridine solution and in the solid state. Attempts to prepare analogous derivatives with 2,2′:6′,2″-terpyridine (terpy) were successful only in the isolation of (terpy)(py)Th(SPh)4, the first terpy compound of thorium. These materials are thermochroic, with color attributed to ligand-to-ligand charge transfer excitations.
In addition, heterometallic compounds with both thorium and uranium have been explored. Four clusters (py)8Th4[Hg(EPh)2]4(μ3-E′)4(μ2-EPh)4(η-EPh)4, (py)8U4[Hg(EPh2)]4(μ3-E′)4(μ2-EPh)4(η-EPh)4 (E’ = S, Se; E = Se) and three cation anion pairs [U8S13I3py17][HgI4][HgI3py], [ThF2bipy2py3][Ag4SePh6], [Th8S13I4py18][HgI4] have been synthesized, isolated, and structurally characterized. These compounds integrate mercury as an external ligand or counter ion instead of a bridging moiety inside the inner core structure as seen in previous lanthanide compounds. 100% occupancy of the mercury moiety in the cubane clusters is not consistent or easily achieved, yet all these compounds are of significant interest when compared to other heterometallic compounds.
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
Subject (authority = ETD-LCSH)
Topic
Actinium compounds
RelatedItem (type = host)
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Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_9523
PhysicalDescription
Form (authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
1 online resource (141 pages) : illustrations
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Note (type = vita)
Includes vita
Note (type = statement of responsibility)
by Marissa Ringgold
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Title
School of Graduate Studies Electronic Theses and Dissertations
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rucore10001600001
Location
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NjNbRU
Identifier (type = doi)
doi:10.7282/t3-6a8p-wb18
Genre (authority = ExL-Esploro)
ETD doctoral
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The author owns the copyright to this work.
RightsHolder (type = personal)
Name
FamilyName
Ringgold
GivenName
Marissa
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2019-01-10 13:05:44
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Marissa Ringgold
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Copyright holder
Affiliation
Rutgers University. School of Graduate Studies
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I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.
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2019-01-16T11:28:08
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2019-01-16T11:28:08
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