Troticene lithiation and platinum-catalyzed hydrosilylation using dimethylsilyl- troticene and ferrocene derivatives
Descriptive
TitleInfo
(ID = T-1)
Title
Troticene lithiation and platinum-catalyzed hydrosilylation using dimethylsilyl- troticene and ferrocene derivatives
Identifier
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(invalid = )
ETD_1776
Identifier
(type = hdl)
http://hdl.rutgers.edu/1782.2/rucore10002600001.ETD.000051319
Language
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LanguageTerm
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(type = code)
eng
Genre
(authority = marcgt)
theses
Subject
(ID = SBJ-1);
(authority = RUETD)
Subject
(ID = SBJ-2);
(authority = ETD-LCSH)
Topic
Organolithium compounds
Subject
(ID = SBJ-3);
(authority = ETD-LCSH)
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
Form
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electronic resource
Extent
xviii, 289 p. : ill.
InternetMediaType
application/pdf
InternetMediaType
text/xml
Note
(type = degree)
Ph.D.
Note
(type = bibliography)
Includes bibliographical references (p. 236-254)
Note
(type = statement of responsibility)
by Rhyan Josephy Soriano Terrado
Name
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(type = family)
Terrado
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(type = given)
Rhyan Joseph
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(type = date)
1978
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(authority = RULIB);
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author
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Rhyan Joseph Terrado
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NamePart
(type = family)
Sheridan
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(type = given)
John
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(authority = RULIB);
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chair
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Advisory Committee
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John Sheridan
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(type = family)
Jäkle
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(type = given)
Frieder
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(authority = RULIB);
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internal member
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Advisory Committee
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Frieder Jäkle
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NamePart
(type = family)
Lalancette
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Roger
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(authority = RULIB);
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internal member
Affiliation
Advisory Committee
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Roger Lalancette
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(ID = NAME-5);
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NamePart
(type = family)
Schnatter
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(type = given)
Wayne
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(authority = RULIB);
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outside member
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Advisory Committee
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Wayne Schnatter
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Rutgers University
Role
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(authority = RULIB);
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degree grantor
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Graduate School - Newark
Role
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(authority = RULIB);
(type = )
school
OriginInfo
DateCreated
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2009
DateOther
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(type = degree)
2009-05
Place
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xx
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TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
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ETD
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(type = host)
TitleInfo
Title
Graduate School - Newark Electronic Theses and Dissertations
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rucore10002600001
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(authority = marcorg);
(displayLabel = Rutgers, The State University of New Jersey)
NjNbRU
Identifier
(type = doi)
doi:10.7282/T39W0FP6
Genre
(authority = ExL-Esploro)
ETD doctoral
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