2026-09-21T22:31:26.209871600Zhttps://opus.uleth.ca/server/oai/requestoai:opus.uleth.ca:10133/66162023-11-03T05:04:26Zcom_10133_3346com_10133_1com_10133_296col_10133_3347col_10133_298
ULethbridge OPUS Repository
supervisor
Hayes, Paul G.
author
Drescher, Sam L.
author
University of Lethbridge. Faculty of Arts and Science
2023-11-02T16:34:01Z
2023-11-02T16:34:01Z
2023
https://hdl.handle.net/10133/6616
The synthesis of iridium 1,5-cyclooctadiene and cyclooctene complexes supported by a monoanionic NNN-pincer ligand is described. The 1,5-cyclooctadiene complexes, ArLIr(COD) (L = 2,5-(iPr2P=NAr)2C4H2N, Ar = Pipp, Dipp, Mes, COD = 1,5-cyclooctadiene) did not react with dihydrogen or silanes, precluding further work into catalytic processes, such as alkane dehydrogenation and hydrosilylation. As such, a more reactive species was sought. PippLIr(COE) (COE = cyclooctene) reacted with dihydrogen and silanes, allowing the synthesis of PippLIr(H)2 and PippLIr(H)(SiR3) (R3 = Et3, HPh2, H2Ph). These complexes were characterized by multinuclear (1H, 13C{1H}, 29Si, 31P{1H}) and 2-dimensional NMR spectroscopy, X-ray crystallography, and elemental analysis. Alternatives to PippLIr(COE), including PippLIr(CO), PippLIr(PPh3), and others were investigated. This was undertaken to avoid competing reactivity with free COE in solution.
The efficacy of PippLIr(H)2 and PippLIr(H)(SiR3) (R3 = Et3, HPh2, H2Ph) as catalysts for alkene hydrogenation and alkane dehydrogenation, and hydrosilylation, respectively, was explored.
en
iridium
NNN-pincer ligand
organometallic chemistry
Small molecule activation by iridium complexes supported by a monoanionic NNN-pincer ligand
Thesis
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
URL
http://localhost:4000/bitstreams/4ae0466d-03c0-4a0d-ace0-2fdcb48adbe7/download
File
MD5
2c691b346871267a4c82ca5e9cfd7f11
3473130
application/pdf
DRESCHER_SAM_MSC_2023.pdf
URL
http://localhost:4000/bitstreams/910848d5-3d8e-41f2-8354-29d423f7ab58/download
File
MD5
b5835e37420bd7db648d80fe8b0f28cf
100592
text/plain
DRESCHER_SAM_MSC_2023.pdf.txt