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Troticene lithiation and platinum-catalyzed hydrosilylation using dimethylsilyl- troticene and ferrocene derivatives

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Text
TitleInfo (ID = T-1)
Title
Troticene lithiation and platinum-catalyzed hydrosilylation using dimethylsilyl- troticene and ferrocene derivatives
SubTitle
PartName
PartNumber
NonSort
Identifier (displayLabel = ); (invalid = )
ETD_1776
Identifier (type = hdl)
http://hdl.rutgers.edu/1782.2/rucore10002600001.ETD.000051319
Language (objectPart = )
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eng
Genre (authority = marcgt)
theses
Subject (ID = SBJ-1); (authority = RUETD)
Topic
Chemistry
Subject (ID = SBJ-2); (authority = ETD-LCSH)
Topic
Organolithium compounds
Subject (ID = SBJ-3); (authority = ETD-LCSH)
Topic
Hydrosilylation
Abstract
The lithiation of troticene was studied. Monolithiation of troticene at 0 °C preferentially occurred at the cycloheptatrienyl (Cht) ligand,1,2 while monolithiation at room temperature preferentially occurred at the cyclopentadienyl (Cp) ligand. Dimethylsilyl-, trimethylstannyl-, diphenylphosphino-, and trimethylsilyl-derivatives were prepared in this manner. The monolithio-cycloheptatrienyl-troticene was found to be less stable at higher temperatures than the monolithio-cyclopentadienyl-troticene. Dilithiation of troticene was readily achieved using 2.5 equiv. n-butyllithium/TMEDA,3 and using an even greater excess of lithiating agent led to greater degrees of lithiation of up to 4 lithiums. Disubstituted Cp ligands are predominantly 1,3-disubstituted, while disubstituted Cht ligands are predominantly 1,4-disubstituted. Substituted troticene derivatives were also lithiated. Just like the 1-pot polylithiation, disubstituted Cp ligands are predominantly 1,3-disubstituted. However, disubstituted Cht ligands are either 1,4- or 1,3-disubstituted.
Dimethylsilyl-troticene derivatives were used in the preparation of troticene- based polymers/oligomers containing silylenevinylenephenylene-/thienylene-bridged metallocene units along with the appropriate model compounds. The regiochemical distributions obtained were consistent with those obtained by Jain and coworkers using dimethylsilyl ferrocene derivatives, with low molecular weights and no metal-metal interaction between the metallocene units.4,5
Hydrosilylation reactions of bis(dimethylsilyl)- ferrocene or troticene gave lower β(E)- to α- olefinic proton ratios compared to dimethylsilyl- ferrocene or troticene, the latter two giving regiochemical distributions consistent with those of 1,4-bis(dimethylsilyl)benzene or dimethylsilylbenzene. These results were consistent regardless of whether phenylacetylene, ethynyltoluene, or ethynylthiophene was used as the alkyne.
A comparison between the hydrosilylation mono-β(E)- and mono-α- adducts of 1,4-bis(dimethylsilyl)benzene and 1,1’-bis(dimethylsilyl)ferrocene with phenylacetylene was done. The hydrosilylation reactions of the mono-β(E)- adducts of both compounds as well as the mono-α- adduct of 1,4-bis(dimethylsilyl)benzene were all consistent with each other, preferring a β(E)- configuration in the hydrosilylation of the second dimethylsilyl-moiety. In contrast, the mono-α- adduct of 1,1’-bis(dimethylsilyl)ferrocene preferred an α- configuration in the hydrosilylation of the second dimethylsilyl-moiety. In addition, the mono-α- adduct of 1,1’-bis(dimethylsilyl)ferrocene was more readily converted into the bis-adducts than the mono-β(E)- adduct. These factors led to an increased amount of α-olefinic protons in hydrosilylation reactions of 1,1’-bis(dimethylsilyl)ferrocene.
PhysicalDescription
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electronic resource
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xviii, 289 p. : ill.
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application/pdf
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text/xml
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Ph.D.
Note (type = bibliography)
Includes bibliographical references (p. 236-254)
Note (type = statement of responsibility)
by Rhyan Josephy Soriano Terrado
Name (ID = NAME-1); (type = personal)
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Terrado
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Rhyan Joseph
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1978
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Rhyan Joseph Terrado
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Sheridan
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John
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chair
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Advisory Committee
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John Sheridan
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Jäkle
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Frieder
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Frieder Jäkle
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Lalancette
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Roger
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Roger Lalancette
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Schnatter
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Wayne
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outside member
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Wayne Schnatter
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Rutgers University
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Graduate School - Newark
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school
OriginInfo
DateCreated (point = ); (qualifier = exact)
2009
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2009-05
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xx
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Rutgers University Electronic Theses and Dissertations
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ETD
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Graduate School - Newark Electronic Theses and Dissertations
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rucore10002600001
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NjNbRU
Identifier (type = doi)
doi:10.7282/T39W0FP6
Genre (authority = ExL-Esploro)
ETD doctoral
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Terrado
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Rhyan Joseph
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Rhayn Joseph Terrado
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Rutgers University. Graduate School - Newark
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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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