Synthetic and structural studies on early transition metal siloxides

dc.contributor.advisorHutton, Alan T
dc.contributor.authorJones, Robert Edward
dc.date.accessioned2017-01-25T14:27:11Z
dc.date.available2017-01-25T14:27:11Z
dc.date.issued1993
dc.date.updated2016-11-22T08:38:53Z
dc.description.abstract[Super- and subscripts in abstract] n-Bu3SiOH was prepared from both n-Bu3SiH and n-Bu3SiCI. Reactions of n-Bu3SiOH with NaH, LiBun, MC15 (M = Ta or Mo) and Cp2MCl2 (Cp = 115-C5H5, M = Ti or Zr) were investigated, in some cases using the base Et3N as a hydrogen chloride acceptor. Na+(QSiPh3r was prepared from the reaction of Ph3SiOH with NaH, but in poor yield. Ph3SiOH was reacted with TaCI5, but the product, if formed at all, was intractable. When Ph3SiOH was reacted with Cp2MC12 (M = Ti or Zr) products were isolated and characterised, viz. [Cp2 TiCl(OSiPh3)]n (n = 1 or 2) and Cp2Zr(OSiPh3)2. Single crystals Cp2Zr(OSiPh3h were studied using X-ray photographic techniques. They crystallise in the monoclinic system with a = 35. 7, b = 10.4, c = 21.1 A, f3 = 97.7 °, V= 7763 A3. A full crystal structure analysis was not possible due to failure of the diffractometer software to locate the monoclinic unit cell determined by photographic methods. Ph3 SiOH was also reacted with Cp 2ZrC12 (Cp = 115-C5Me5) and the product was tentatively assigned to be Cp 2Zr(OSiPh3h as a pure sample could not be obtained. An interesting spirocompound, Ti[OSiPh2(0SiPh2)30h, was prepared from Ph2Si(0Hh and Ti(n-Bu0)4 and the crystal structure determined by X-ray crystallography. It crystallises in the monoclinic system, space group P21/n, a = 13.805(5), b = 27.545(5), c = 23.476(9) A, f3 = 94.41(3) 0 , V= 8901(5) A3, Z = 4, R = 0.0831 for 5528 reflections with Ire/> 2a(Iref).
dc.identifier.apacitationJones, R. E. (1993). <i>Synthetic and structural studies on early transition metal siloxides</i>. (). University of Cape Town ,Faculty of Science ,Department of Chemistry. Retrieved from http://hdl.handle.net/11427/23079en_ZA
dc.identifier.chicagocitationJones, Robert Edward. <i>"Synthetic and structural studies on early transition metal siloxides."</i> ., University of Cape Town ,Faculty of Science ,Department of Chemistry, 1993. http://hdl.handle.net/11427/23079en_ZA
dc.identifier.citationJones, R. 1993. Synthetic and structural studies on early transition metal siloxides. University of Cape Town.en_ZA
dc.identifier.ris TY - Thesis / Dissertation AU - Jones, Robert Edward AB - [Super- and subscripts in abstract] n-Bu3SiOH was prepared from both n-Bu3SiH and n-Bu3SiCI. Reactions of n-Bu3SiOH with NaH, LiBun, MC15 (M = Ta or Mo) and Cp2MCl2 (Cp = 115-C5H5, M = Ti or Zr) were investigated, in some cases using the base Et3N as a hydrogen chloride acceptor. Na+(QSiPh3r was prepared from the reaction of Ph3SiOH with NaH, but in poor yield. Ph3SiOH was reacted with TaCI5, but the product, if formed at all, was intractable. When Ph3SiOH was reacted with Cp2MC12 (M = Ti or Zr) products were isolated and characterised, viz. [Cp2 TiCl(OSiPh3)]n (n = 1 or 2) and Cp2Zr(OSiPh3)2. Single crystals Cp2Zr(OSiPh3h were studied using X-ray photographic techniques. They crystallise in the monoclinic system with a = 35. 7, b = 10.4, c = 21.1 A, f3 = 97.7 °, V= 7763 A3. A full crystal structure analysis was not possible due to failure of the diffractometer software to locate the monoclinic unit cell determined by photographic methods. Ph3 SiOH was also reacted with Cp 2ZrC12 (Cp = 115-C5Me5) and the product was tentatively assigned to be Cp 2Zr(OSiPh3h as a pure sample could not be obtained. An interesting spirocompound, Ti[OSiPh2(0SiPh2)30h, was prepared from Ph2Si(0Hh and Ti(n-Bu0)4 and the crystal structure determined by X-ray crystallography. It crystallises in the monoclinic system, space group P21/n, a = 13.805(5), b = 27.545(5), c = 23.476(9) A, f3 = 94.41(3) 0 , V= 8901(5) A3, Z = 4, R = 0.0831 for 5528 reflections with Ire/> 2a(Iref). DA - 1993 DB - OpenUCT DP - University of Cape Town LK - https://open.uct.ac.za PB - University of Cape Town PY - 1993 T1 - Synthetic and structural studies on early transition metal siloxides TI - Synthetic and structural studies on early transition metal siloxides UR - http://hdl.handle.net/11427/23079 ER - en_ZA
dc.identifier.urihttp://hdl.handle.net/11427/23079
dc.identifier.vancouvercitationJones RE. Synthetic and structural studies on early transition metal siloxides. []. University of Cape Town ,Faculty of Science ,Department of Chemistry, 1993 [cited yyyy month dd]. Available from: http://hdl.handle.net/11427/23079en_ZA
dc.language.isoeng
dc.publisher.departmentDepartment of Chemistryen_ZA
dc.publisher.facultyFaculty of Scienceen_ZA
dc.publisher.institutionUniversity of Cape Town
dc.subject.otherChemistry
dc.titleSynthetic and structural studies on early transition metal siloxides
dc.typeThesis
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