Full metadata
Title
Synthesis and reactivity of group 9 complexes featuring redox non-innocent ligands
Description
The addition of aminoalkyl-substituted 2,6-bis(imino)pyridine (or pyridine diimine, PDI) ligands to [(COD)RhCl]2 (COD = 1,5-cyclooctadiene) resulted in the formation of rhodium monochloride complexes with the general formula (NPDI)RhCl (NPDI = iPr2NEtPDI or Me2NPrPDI). The investigation of (iPr2NEtPDI)RhCl and (Me2NPrPDI)RhCl by single crystal X-ray diffraction verified the absence of amine arm coordination and a pseudo square planar geometry about rhodium. Replacement of the chloride ligand with an outer-sphere anion was achieved by adding AgBF4 directly to (iPr2NEtPDI)RhCl to form [(iPr2NEtPDI)Rh][BF4]. Alternatively, this complex was prepared upon chelate addition following the salt metathesis reaction between AgBF4 and [(COD)RhCl]2. Using the latter method, both [(NPDI)Rh][BF4] complexes were isolated and found to exhibit κ4-N,N,N,N-PDI coordination regardless of arm length or steric bulk. In contrast, the metallation of PPDI chelates featuring alkylphosphine imine substituents (PPDI = Ph2PEtPDI or Ph2PPrPDI) resulted in the formation of cationic complexes featuring κ5-N,N,N,P,P-PDI coordination in all instances, [(PPDI)Rh][X] (X = Cl, BF4). Adjusting the metallation stoichiometry allowed the preparation of [(Ph2PPrPDI)Rh][(COD)RhCl2], which was characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction.
Date Created
2016
Contributors
- Levin, Hagit Ben-Daat (Author)
- Trovitch, Ryan J (Thesis advisor)
- Gould, Ian R (Committee member)
- Ghirlanda, Giovanna (Committee member)
- Arizona State University (Publisher)
Topical Subject
Resource Type
Extent
vii, 71 pages : illustrations (some color)
Language
eng
Copyright Statement
In Copyright
Primary Member of
Peer-reviewed
No
Open Access
No
Handle
https://hdl.handle.net/2286/R.I.38406
Statement of Responsibility
by Hagit Ben-Daat Levin
Description Source
Retrieved on June 9, 2016
Level of coding
full
Note
thesis
Partial requirement for: M.S., Arizona State University, 2016
bibliography
Includes bibliographical references (pages 62-69)
Field of study: Chemistry
System Created
- 2016-06-01 08:04:46
System Modified
- 2021-08-30 01:24:43
- 3 years 2 months ago
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