Some new inorganic and organometallic derivatives of methylcyclosiloxanes have been prepared and characterized by IR, MS and ('1)H NMR. Compounds, {CH(,3)(Br)SiO}(,3) and {CH(,3)(Br)SiO}(,4) were prepared by cleavage of silicon-phenyl bond with bromine at low temperature. The reaction of {CH(,3)(Br)SiO}(,3) with Na(sec-butyl)(,3)BH at low temperature produced the highly reactive trimer, {CH(,3)(H)SiO}(,3). Compounds {CH(,3)(Co(CO)(,4))SiO}(,4), {CH(,3)(Fe(CO)(,2)(eta)('5)-C(,5)H(,5))SiO}(,4), and {CH(,3)(Co(CO)(,4)SiO}(,5) were prepared by the hydrogen elimination reaction of {CH(,3)(H)SiO}(,n), n = 4 and 5 with Co(,2)(CO)(,8) and {Fe(CO)(,2)(eta)('5)-C(,5)H(,5)}(,2). It was also possible to isolate the compound {CH(,3)(Co(CO)(,4))SiO}(,1){CH(,3)(Fe(CO)(,2)(eta)('5)-C(,5)H(,5))SiO}(,3) by reacting {CH(,3)(H)SiO}(,1){CH(,3)(Fe(CO)(,2)(eta)('5)-C(,5)H(,5))SiO}(,3) with a stoichiometric amount of Co(,2)(CO)(,8). A detailed study of mass spectra of {CH(,3)(R)SiO}(,n), where R = H, (n = 4, 5, and 6), R = C(,6)H(,5), (n = 3 and 4), R = Br, (n = 3 and 4), R = Co(CO)(,4), (n = 4 and 5) and R = Fe(CO)(,2)(eta)('5)-C(,5)H(,5), (n = 4) was achieved. Compounds R = Co(CO)(,4) show stepwise loss of all CO groups from ions {M}('+(.)), {M-Co(CO)(,4)}('+), and also {M}('++). A simple empirical approach based on the chemical environment of methyl protons was used to assign ('1)H NMR spectra of geometric isomers of substituted methylcyclosiloxanes. The total assignment of ('1)H NMR spectra allowed the determination of the isomeric composition of most new compounds mentioned above.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.71826 |
| Date | January 1983 |
| Creators | Pelletier, Emilien. |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 000186813, proquestno: AAINK64509, Theses scanned by UMI/ProQuest. |
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