Title Information
Title
Synergistic Effect of X-ray Crystallography and Solution NMR on Structural Characterization of Organolithium Complexes
Name: Personal
Name Part
Guang, Jie
Role
Role Term: Text
creator
Origin Information
Copyright Date
2015
Physical Description
Extent
xvi, 135 p.
digitalOrigin
born digital
Note
Thesis (Ph.D. -- Brown University (2015)
Name: Personal
Name Part
Williard, Paul
Role
Role Term: Text
Director
Name: Personal
Name Part
Basu, Amit
Role
Role Term: Text
Reader
Name: Personal
Name Part
Seto, Christopher
Role
Role Term: Text
Reader
Name: Corporate
Name Part
Brown University. Chemistry
Role
Role Term: Text
sponsor
Genre (aat)
theses
Abstract
Structural characterization of organolithium compounds in solution is an important but challenging task. Solution nuclear magnetic resonance (NMR) and X-ray crystallography are two of the most powerful and widely used methods to overcome this challenge. However the correct and reliable interpretation for the NMR spectra of organolithium complexes is difficult, because a) NMR samples contain impurities because organolithium compounds are air-sensitive; b) even pure samples can be mixture as organolithium reagents form various oligomers and mixed aggregates; c) peak assignments in NMR spectra can be ambiguous as different oligomers and aggregates may have very similar structures and present duplicate absorbance. On the other hand, the limitation of X-ray crystallography is also obvious: as a solid-state method, X-ray diffraction (XRD) does not offer structural information for the liquid state. However the combination of NMR and XRD presents a synergistic effect, because NMR helps optimize the preparation conditions of various crystals and X-ray analysis offers trustworthy structural information and unambiguous assignment to partial NMR spectra. This combination becomes the crucial foundation for the interpretation of the NMR data. A variety of systems has been studied by this NMR/XRD integrated protocal including lithium enolates, lithium amide bases and perfluoro Grignard reagents. This thesis incorporates examples that illustrate the application of X-ray crystallography and a variety of multi nuclei (1H, 2H, 6Li, 13C, 19F) NMR techniques including referenced diffusion-ordered NMR spectroscopy (DOSY) to structural analysis.
Subject
Topic
organolithium
Subject
Topic
solution NMR
Subject (FAST) (authorityURI="http://id.worldcat.org/fast", valueURI="http://id.worldcat.org/fast/1047962")
Topic
Organolithium compounds
Subject (FAST) (authorityURI="http://id.worldcat.org/fast", valueURI="http://id.worldcat.org/fast/1181820")
Topic
X-ray crystallography
Record Information
Record Content Source (marcorg)
RPB
Record Creation Date (encoding="iso8601")
20150601
Language
Language Term: Code (ISO639-2B)
eng
Language Term: Text
English
Identifier: DOI
10.7301/Z0NC5ZKV
Access Condition: rights statement (href="http://rightsstatements.org/vocab/InC/1.0/")
In Copyright
Access Condition: restriction on access
Collection is open for research.
Type of Resource (primo)
dissertations