investigation of co2 insertion into lanthanide amides
TRANSCRIPT
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University of New MexicoUNM Digital Repository
Chemistry ETDs Electronic Theses and Dissertations
2-9-2010
Investigation of CO2 insertion into lanthanideamides, alkoxides, and mixed amide/alkoxidesLeigh Anna M. Ottley
Follow this and additional works at: https://digitalrepository.unm.edu/chem_etds
This Thesis is brought to you for free and open access by the Electronic Theses and Dissertations at UNM Digital Repository. It has been accepted forinclusion in Chemistry ETDs by an authorized administrator of UNM Digital Repository. For more information, please contact [email protected].
Recommended CitationOttley, Leigh Anna M.. "Investigation of CO2 insertion into lanthanide amides, alkoxides, and mixed amide/alkoxides." (2010).https://digitalrepository.unm.edu/chem_etds/46
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INVESTIGATION OF CO2 INSERTION INTO LANTHANIDE AMIDES, ALKOXIDES, AND MIXED AMIDE/ALKOXIDES
BY
LEIGH ANNA M. OTTLEY
BACHELORS OF SCIENCE IN CHEMISTRY University of New Mexico
2006
THESIS
Submitted in Partial Fulfillment of the Requirements for the Degree of
Master of Science
Chemistry and Chemical Biology
The University of New Mexico Albuquerque, New Mexico
December, 2009
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!!!""
©2009, Leigh Anna Ottley
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To my loving family and friends for their encouragement and support throughout all my endeavors.
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ACKNOWLEDGEMENTS
I would like to thank my advisor, Professor Rick Kemp, for his support and direction
over the course of my academic career, as well as my mentor, Dr. Timothy J. Boyle, who
has helped me get where I am today both academically and professionally. I would also
like to thank Dr. Diane Dickie, Dr. Constantine Stewart, and Dr. Todd Alam for their
contributions and guidance. In addition, I would like to thank Dr. Bernadette Hernandez-
Sanchez for invaluable conversations and advice. Finally, I would like to thank the Boyle
group for their hard work and continuous support.
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INVESTIGATION OF CO2 INSERTION INTO LANTHANIDE AMIDES, ALKOXIDES, AND MIXED AMIDE/ALKOXIDES
BY
LEIGH ANNA M. OTTLEY
ABSTRACT OF THESIS
Submitted in Partial Fulfillment of the Requirements for the Degree of
Masters of Science
Chemistry and Chemical Biology
The University of New Mexico Albuquerque, New Mexico
December, 2009
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INVESTIGATION OF CO2 INSERTION INTO LANTHANIDE AMIDES, ALKOXIDES, AND MIXED AMIDE/ALKOXIDES
Leigh Anna M. Ottley
B.S., Chemistry, University of New Mexico, 2006
M.S., Chemistry and Chemical Biology, University of New Mexico, 2009
ABSTRACT
A novel set of lanthanide (Ln) alkoxycarbonates, [Ln(!-CO2-DBP)(DBP)2]2
where Ln = lanthanide; and DBP = OC6H3-2,6-C(CH3)3, were isolated from a systematic
study of the insertion of CO2(g) (referred to as CO2) into the Ln-O bonds of a series of
new lanthanide alkoxides, Ln(OR)3. This study was undertaken to determine if the
deleterious metal carbonate [M(CO3)y] formation that promotes higher thermal budgets
during processing could be avoided. While processing controls can reduce the formation
of the M(CO3)y phases, this is not always effective, and preventing the formation of these
phases is of interest. Since CO2 insertion into transition metal alkoxides has been
extensively studied and many structures reported, this research focused on CO2 insertion
into the less-studied Ln-O bonds of Ln(OR)3. Initially a series of lanthanide amides
[Ln(NR2)3 where R = SiMe3 and Ln = Ce (1), Sm (2), Dy (3), Yb (4), and Lu (5)] were
synthesized following established routes.4-6 Subsequent conversion of the Ln(NR2)3
species into a series of Ln(OR)3 was achieved by an amide/alcohol exchange route
resulting in Ln(DBP)3 (Ln = Ce (6), Sm (7), Dy (8), Yb (9), and Lu (10); DBP = 2,6-di-
tert-butylphenoxide).7, 8 Once isolated, CO2 at low pressure (<5 psig) and ambient
temperature was introduced to the Ln(OR)3 species to form a novel family of lanthanide
alkoxycarbonate compounds identified as [Ln(!- O2C-DBP)(DBP)2]2 (Ln = Ce (11), Sm
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(12), Dy (13), Yb (14), and Lu (15)). Surprisingly, CO2 did not insert into all of the Ln-
O bonds, indicating that this process might be more controllable than initially expected.
Higher-pressure CO2 experiments yielded the same carbonate compounds. Further
manipulation of the ligand set, as a means to control CO2 insertion, was explored by
using a mixed amide/alkoxide precursor generated in situ. This resulted in the formation
of an unusual complex, Sm4(!-CO3)2(!-O)2(DBP)4(THF)2(!-DBP) (16). From this
fundamental study, it has been shown that the ligand may be able to impact the degree of
CO2 insertion into Ln-O bonds. The synthesis and characterization of 1 - 16, as well as
future implications of this work, will be discussed in detail.
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![Page 16: Investigation of CO2 insertion into lanthanide amides](https://reader033.vdocuments.mx/reader033/viewer/2022041600/6252cf3638493479db797ac0/html5/thumbnails/16.jpg)
#!
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1.4 Families of Lanthanide Compounds Selected for this Study
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1.5 Summary
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3.2 Alkoxide Synthesis and Characterization
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3.6 CO2 Insertion into Mixed Amide/Alkoxide in Solution
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4.5 Conclusion
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5.1 Appendix A: TABLES
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c /s1* ^^MF^HW/^F1! ^^MFH[H/^>1! ^^M]`Z^/^W1! ^HMFHa/W1! >^M^[H/H1!
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