University of Illinois Urbana-Champaign

Synthetic methods and studies of some 10-Y-5 and 12-Y-6 hypervalent main group element species of group IIIB

Hoglen, Dean Kent

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Description

Title
Synthetic methods and studies of some 10-Y-5 and 12-Y-6 hypervalent main group element species of group IIIB
Author(s)
Hoglen, Dean Kent
Issue Date
1990
Doctoral Committee Chair(s)
Martin, J.C.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Language
eng
Abstract
  • p-t-Butylhexafluorocumylthiol and N,N-dimethylhexafluorocumylamine were synthesized and found not to undergo ortho-lithiation. p-t-Butylhexafluorocumylthiol forms several products upon treatment with an alkyllithium reagent and N,N-dimethylhexafluorocumylamine undergoes meta-lithiation upon treatment with sec-butyllithium in the presence of TMEDA. Evidence for the formation of stable hypervalent phosphorus and silicon species using 1,3-bis(2$\sp\prime$-pyridylimino)isoindoline as a tridentate ligand was obtained.
  • New synthetic routes were developed for 4-t-butyl-2,6-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)pyridine and 2-amino-4-(t-butyl)pyridine which allowed their synthesis on a large scale, with reasonable amounts formed. The former was synthesized by ortho-lithiation of 4-t-butyl-2-(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-pyridine-1-oxide and treatment with hexafluoroacetone. The latter was synthesized by nucleophilic aromatic substitution on 2-bromo-4-t-butylpyridine using sodium amide as nucleophile.
  • Because a new melting point reflecting a new crystal structure for 10-t-butyl-1-chloro-3,3,7,7-tetrakis(trifluoromethyl)-4,6-benzo-5-azonia-1-borata-2,8-dioxabicyclo- (3,3,0) octane resulted in a change in solubility and reactivity, new routes to hypervalent 12-B-6 and 10-B-5 species were explored, and were not successful.
  • N,N,N-tributylbutanaminium(OC-6-11$\sp\prime$)-bis (4-(1,1-dimethylethyl)-$\alpha,\alpha,\alpha\sp\prime\alpha\sp\prime$-tetrakis(trifluoromethyl)-2,6-pyridinedimethanolato(2-)N1,O$\alpha$,O$\alpha\sp\prime$) aluminum, a 12-Al-6 anionic species was synthesized and experimentally examined. Neutral mono-protonated and mono-methylated products of this anion were synthesized and studied. X-ray crystallography was used to establish the structure of the octahedral 12-Al-6 species and its protonated analogue. The protonated species was a distorted octahedral species with the proton hydrogen-bonding two of the apical oxygens.
Type of Resource
text
Permalink
http://hdl.handle.net/2142/20053
Copyright and License Information
Copyright 1990 Hoglen, Dean Kent

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