{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21979"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21979","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Transition metal allyls and hydrides as chemical vapor deposition precursors","abstract":"Thin films of high purity palladium can be prepared at low temperature (250$\\sp\\circ$C) metal-organic chemical vapor deposition of bis(allyl)palladium or (cyclopentadienyl)(allyl)palladium.","abstract_html":"Thin films of high purity palladium can be prepared at low temperature (250$\\sp\\circ$C) metal-organic chemical vapor deposition of bis(allyl)palladium or (cyclopentadienyl)(allyl)palladium.","abstract_has_math":true,"creators":["Gozum, John Ekrem"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:25:06Z","date_published":"2011-05-07T13:25:06Z","updated_at":"2026-07-22T22:25:19Z","subjects":["Chemistry, Inorganic","Physics, Electricity and Magnetism","Engineering, Materials Science"],"languages":["eng"],"rights":["Copyright 1991 Gozum, John Ekrem"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9136603","(UMI)AAI9136603"],"render_values":[{"text":"AAI9136603","href":null,"code":true},{"text":"(UMI)AAI9136603","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21979","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Gozum, John Ekrem"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:25:06Z","10000-01-01","1991"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Inorganic","Physics, Electricity and Magnetism","Engineering, Materials Science"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1991 Gozum, John Ekrem"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9136603","(UMI)AAI9136603","http://hdl.handle.net/2142/21979"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Thin films of high purity palladium can be prepared at low temperature (250$\\sp\\circ$C) metal-organic chemical vapor deposition of bis(allyl)palladium or (cyclopentadienyl)(allyl)palladium.","Metal sulfide films may be deposited from the precursors $\\rm Fe\\sb2S\\sb2(CO)\\sb6$ and Ti(S-t-Bu)$\\sb4$ to give thin films of iron sulfide and titanium disulfide at low temperature.","CVD of Ti(BH$\\sb4)\\sb3$(dme) at 200$\\sp\\circ$C resulted in deposition of thin films of TiB$\\sb2$. The AES data establish the films as TiB$\\sb{2.07}$ with less than 5% carbon and oxygen in the film interior.","Passage of Zr(BH$\\sb4)\\sb4$ or Hf(BH$\\sb4)\\sb4$ through a hot zone at 250$\\sp\\circ$C resulted in deposition of thin films of MB$\\sb2$.","In order to trap some of the hydride species that may be formed from the CVD of Zr(BH$\\sb4)\\sb4$ and Hf(BH$\\sb4)\\sb4$, these precursors were thermolyzed in the presence of small alkyl phosphines. Treatment of the zirconium and hafnium tetrahydroborate complexes M(BH$\\sb4)\\sb4$ with trimethylphosphine yields crystals of the new polyhydride $\\rm Zr\\sb2H\\sb3(BH\\sb4)\\sb5(PMe\\sb3)\\sb2$ and $\\rm Hf\\sb2H\\sb3(BH\\sb4)\\sb5(PMe\\sb3)\\sb2$. Single crystal X-ray diffraction studies of the complexes reveal a distinctly asymmetric dinuclear structure bridged by three hydrogen atoms.","Treatment of $\\rm Zr(BH\\sb4)\\sb4$ or $\\rm Hf(BH\\sb4)\\sb4$ with trimethylphosphine for extended reaction times has given two new polyhydrides of stoichiometry $\\rm M\\sb3H\\sb6(BH\\sb4)\\sb6(PMe\\sb3)\\sb4$. The variable temperature $\\sp1$H, $\\sp{31}$P, and $\\sp{11}$B NMR data suggest that these trinuclear compounds contain a non-cyclic M($\\mu$-H)$\\sb3$M($\\mu$-H)$\\sb3$M backbone with the phosphine and tetrahydroborate ligands distributed in 2:2:0 and 2:1:3 ratios among the three metal centers. This suggestion has been confirmed by a single crystal X-ray structure.","Treatment of the M(BH$\\sb4)\\sb4$ complexes with the bidentate phosphine 1,2-bis(dimethyl-phosphino)ethane (dmpe) gives mononuclear hydrides of stoichiometry MH(BH$\\sb4)\\sb3$(dmpe)$\\sb2$ or $\\rm MH\\sb2(BH\\sb4)\\sb2(dmpe)\\sb2$ depending on the conditions.","Treatment of the polyhydride complexes $\\rm M\\sb2H\\sb3(BH\\sb4)\\sb5(PMe\\sb3)\\sb2$ with dmpe has given two new group 4 polyhydrides of stoichiometry $\\rm M\\sb2H\\sb4(BH\\sb4)\\sb4(dmpe)\\sb2$. The variable temperature NMR data suggest that these dinuclear compounds contain a M($\\mu$-H)$\\sb3$M backbone with the phosphine and tetrahydroborate ligands distributed in 2:0 and 1:3 ratios among the two metal centers; this has been confirmed by the single crystal X-ray structure. A terminal hydride is positioned in between the two bidentate dmpe ligands. A dynamic process exchanges these hydride environments, and a likely mechanism for this process has been proposed.","Made available in DSpace on 2011-05-07T13:25:06Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9136603.pdf: 6988788 bytes, checksum: 5692848bb726e3d9049cba3c781541bd (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:54:30Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:25:20-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Transition metal allyls and hydrides as chemical vapor deposition precursors"]}]}],"canonical_facts":{"dc:creator":["Gozum, John Ekrem"],"dc:date":["2011-05-07T13:25:06Z","10000-01-01","1991"],"dc:description":["Thin films of high purity palladium can be prepared at low temperature (250$\\sp\\circ$C) metal-organic chemical vapor deposition of bis(allyl)palladium or (cyclopentadienyl)(allyl)palladium.","Metal sulfide films may be deposited from the precursors $\\rm Fe\\sb2S\\sb2(CO)\\sb6$ and Ti(S-t-Bu)$\\sb4$ to give thin films of iron sulfide and titanium disulfide at low temperature.","CVD of Ti(BH$\\sb4)\\sb3$(dme) at 200$\\sp\\circ$C resulted in deposition of thin films of TiB$\\sb2$. The AES data establish the films as TiB$\\sb{2.07}$ with less than 5% carbon and oxygen in the film interior.","Passage of Zr(BH$\\sb4)\\sb4$ or Hf(BH$\\sb4)\\sb4$ through a hot zone at 250$\\sp\\circ$C resulted in deposition of thin films of MB$\\sb2$.","In order to trap some of the hydride species that may be formed from the CVD of Zr(BH$\\sb4)\\sb4$ and Hf(BH$\\sb4)\\sb4$, these precursors were thermolyzed in the presence of small alkyl phosphines. Treatment of the zirconium and hafnium tetrahydroborate complexes M(BH$\\sb4)\\sb4$ with trimethylphosphine yields crystals of the new polyhydride $\\rm Zr\\sb2H\\sb3(BH\\sb4)\\sb5(PMe\\sb3)\\sb2$ and $\\rm Hf\\sb2H\\sb3(BH\\sb4)\\sb5(PMe\\sb3)\\sb2$. Single crystal X-ray diffraction studies of the complexes reveal a distinctly asymmetric dinuclear structure bridged by three hydrogen atoms.","Treatment of $\\rm Zr(BH\\sb4)\\sb4$ or $\\rm Hf(BH\\sb4)\\sb4$ with trimethylphosphine for extended reaction times has given two new polyhydrides of stoichiometry $\\rm M\\sb3H\\sb6(BH\\sb4)\\sb6(PMe\\sb3)\\sb4$. The variable temperature $\\sp1$H, $\\sp{31}$P, and $\\sp{11}$B NMR data suggest that these trinuclear compounds contain a non-cyclic M($\\mu$-H)$\\sb3$M($\\mu$-H)$\\sb3$M backbone with the phosphine and tetrahydroborate ligands distributed in 2:2:0 and 2:1:3 ratios among the three metal centers. This suggestion has been confirmed by a single crystal X-ray structure.","Treatment of the M(BH$\\sb4)\\sb4$ complexes with the bidentate phosphine 1,2-bis(dimethyl-phosphino)ethane (dmpe) gives mononuclear hydrides of stoichiometry MH(BH$\\sb4)\\sb3$(dmpe)$\\sb2$ or $\\rm MH\\sb2(BH\\sb4)\\sb2(dmpe)\\sb2$ depending on the conditions.","Treatment of the polyhydride complexes $\\rm M\\sb2H\\sb3(BH\\sb4)\\sb5(PMe\\sb3)\\sb2$ with dmpe has given two new group 4 polyhydrides of stoichiometry $\\rm M\\sb2H\\sb4(BH\\sb4)\\sb4(dmpe)\\sb2$. The variable temperature NMR data suggest that these dinuclear compounds contain a M($\\mu$-H)$\\sb3$M backbone with the phosphine and tetrahydroborate ligands distributed in 2:0 and 1:3 ratios among the two metal centers; this has been confirmed by the single crystal X-ray structure. A terminal hydride is positioned in between the two bidentate dmpe ligands. A dynamic process exchanges these hydride environments, and a likely mechanism for this process has been proposed.","Made available in DSpace on 2011-05-07T13:25:06Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9136603.pdf: 6988788 bytes, checksum: 5692848bb726e3d9049cba3c781541bd (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:54:30Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:25:20-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9136603","(UMI)AAI9136603","http://hdl.handle.net/2142/21979"],"dc:language":["eng"],"dc:rights":["Copyright 1991 Gozum, John Ekrem"],"dc:subject":["Chemistry, Inorganic","Physics, Electricity and Magnetism","Engineering, Materials Science"],"dc:title":["Transition metal allyls and hydrides as chemical vapor deposition precursors"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:19Z"}