{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/23041"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/23041","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"\"Low-valent early transition metal complexes stabilized by the chelating tripod phosphine ligand ( t-butyl)tris((dimethylphosphino)methyl);silane (\"\"trimpsi\"\")\"","abstract":"\"The organometallic chemistry of the early first-row metals has been extended through the use of a new tridentate phosphine ligand, Bu$\\sp{\\rm t}$Si(CH$\\sb2$PMe$\\sb2$)$\\sb3$, or \"\"trimpsi\"\". The starting materials (trimpsi)TiCl$\\sb3$(thf), (trimpsi)VCl$\\sb3$(thf), (trimpsi)CrCl$\\sb3$, and (trimpsi)ZrCl$\\sb4$(dme) have been used to prepare new carbonyl, arene, and alkyl complexes of the early transition metals.\"","abstract_html":""The organometallic chemistry of the early first-row metals has been extended through the use of a new tridentate phosphine ligand, Bu$\\sp{\\rm t}$Si(CH$\\sb2$PMe$\\sb2$)$\\sb3$, or ""trimpsi"". The starting materials (trimpsi)TiCl$\\sb3$(thf), (trimpsi)VCl$\\sb3$(thf), (trimpsi)CrCl$\\sb3$, and (trimpsi)ZrCl$\\sb4$(dme) have been used to prepare new carbonyl, arene, and alkyl complexes of the early transition metals."","abstract_has_math":true,"creators":["Gardner, Thomas George"],"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":"2011-05-07T14:00:02Z","date_published":"2011-05-07T14:00:02Z","updated_at":"2026-07-22T22:25:21Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1989 Gardner, Thomas George"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9010859","(UMI)AAI9010859"],"render_values":[{"text":"AAI9010859","href":null,"code":true},{"text":"(UMI)AAI9010859","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/23041","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Gardner, Thomas George"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T14:00:02Z","10000-01-01","1989"]},{"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"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1989 Gardner, Thomas George"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9010859","(UMI)AAI9010859","http://hdl.handle.net/2142/23041"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["\"The organometallic chemistry of the early first-row metals has been extended through the use of a new tridentate phosphine ligand, Bu$\\sp{\\rm t}$Si(CH$\\sb2$PMe$\\sb2$)$\\sb3$, or \"\"trimpsi\"\". The starting materials (trimpsi)TiCl$\\sb3$(thf), (trimpsi)VCl$\\sb3$(thf), (trimpsi)CrCl$\\sb3$, and (trimpsi)ZrCl$\\sb4$(dme) have been used to prepare new carbonyl, arene, and alkyl complexes of the early transition metals.\"","The 18-electron titanium carbonyl complex, (trimpsi)-Ti(CO)$\\sb4$, is prepared by reductive carbonylation of (trimpsi)TiCl$\\sb3$(thf) with sodium naphthalenide. It has a carbonyl $\\sp{13}$C NMR chemical shift which is unusually far downfield, and an abnormally low IR stretching force constant, indicting unusually strong metal-to-ligand $\\pi$ back-bonding. Although titanium(0) is only d$\\sp4$, its relatively low effective nuclear charge places the d orbitals at unusually high energies, promoting better $\\pi$ overlap with the ligand $\\pi\\sp\\*$ orbitals. Unlike the few known low-valent titanium carbonyls, (trimpsi)-Ti(CO)$\\sb4$ shows remarkable thermal and oxidative stability. Similar conclusions have been made for the related complexes (trimpsi)Zr(CO)$\\sb4$ and (trimpsi)VH(CO)$\\sb3$.","The 16-electron (trimpsi)Ti($\\eta\\sp6$-naphthalene) and the 17-electron (trimpsi)V($\\eta\\sp6$-naphthalene) are rare examples of early transition metal arene complexes, and are isolable intermidiates in the preparation of the trimpsi metal carbonyls. Unlike other known titanium(0) arene complexes, (trimpsi)Ti($\\eta\\sp6$-naphthalene) is paramagnetic. The X-ray crystal structure of (trimpsi)Ti($\\eta\\sp6$-naphthalene) shows a coordinated naphthalene ring that is warped at a dihedral angle of 12.4$\\sp\\circ$, whereas Ti(C$\\sb6$H$\\sb6$)$\\sb2$ and Ti(C$\\sb6$H$\\sb5$CH$\\sb3$)$\\sb2$ have planar arene rings, and the naphthalene ring in (trimpsi)V-($\\eta\\sp6$-naphthalene) has a dihedral angle of only 5.1$\\sp\\circ$. Like the group 4 carbonyls, (trimpsi)Ti($\\eta\\sp6$-naphthalene) exhibits exceptionally strong & back-bonding from the filled Ti 3d$\\sb{\\rm x}\\sp2\\sb{\\rm -y}\\sp2$ orbital to the naphthalene L.U.M.O. The ring warps such that the carbon atoms with the greatest L.U.M.O. coefficient have the shortest metal-carbon distances. In general, the greater the dihedral angle, the stronger the $\\delta$ back-bonding.","The 15-electron complexes (trimpsi)CrEt$\\sb3$ and (trimpsi)-CrBu$\\sp{\\rm n}\\sb3$ are thermally stable at room temperature, and undergo $\\beta$-elimination only at elevated temperatures. The $n$-butyl ligands in (trimpsi)CrBu$\\sp{\\rm n}\\sb3$ are structurally similar to those of $n$-butyl-main group compounds. These trialkylchromium(III) complexes are poor ethylene polymerization catalysts. The vanadium(III) alkyl (trimpsi)V(CH$\\sb2$SiMe$\\sb3$)Cl$\\sb2$ has also been prepared.","The chemistry of trimpsi organoyttrium complexes has also been briefly explored.","Made available in DSpace on 2011-05-07T14:00:02Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9010859.pdf: 5336417 bytes, checksum: ff9592561cd3fce6b904b1882b38e870 (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:01:46Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:29:19-05:00 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":["\"Low-valent early transition metal complexes stabilized by the chelating tripod phosphine ligand ( t-butyl)tris((dimethylphosphino)methyl);silane (\"\"trimpsi\"\")\""]}]}],"canonical_facts":{"dc:creator":["Gardner, Thomas George"],"dc:date":["2011-05-07T14:00:02Z","10000-01-01","1989"],"dc:description":["\"The organometallic chemistry of the early first-row metals has been extended through the use of a new tridentate phosphine ligand, Bu$\\sp{\\rm t}$Si(CH$\\sb2$PMe$\\sb2$)$\\sb3$, or \"\"trimpsi\"\". The starting materials (trimpsi)TiCl$\\sb3$(thf), (trimpsi)VCl$\\sb3$(thf), (trimpsi)CrCl$\\sb3$, and (trimpsi)ZrCl$\\sb4$(dme) have been used to prepare new carbonyl, arene, and alkyl complexes of the early transition metals.\"","The 18-electron titanium carbonyl complex, (trimpsi)-Ti(CO)$\\sb4$, is prepared by reductive carbonylation of (trimpsi)TiCl$\\sb3$(thf) with sodium naphthalenide. It has a carbonyl $\\sp{13}$C NMR chemical shift which is unusually far downfield, and an abnormally low IR stretching force constant, indicting unusually strong metal-to-ligand $\\pi$ back-bonding. Although titanium(0) is only d$\\sp4$, its relatively low effective nuclear charge places the d orbitals at unusually high energies, promoting better $\\pi$ overlap with the ligand $\\pi\\sp\\*$ orbitals. Unlike the few known low-valent titanium carbonyls, (trimpsi)-Ti(CO)$\\sb4$ shows remarkable thermal and oxidative stability. Similar conclusions have been made for the related complexes (trimpsi)Zr(CO)$\\sb4$ and (trimpsi)VH(CO)$\\sb3$.","The 16-electron (trimpsi)Ti($\\eta\\sp6$-naphthalene) and the 17-electron (trimpsi)V($\\eta\\sp6$-naphthalene) are rare examples of early transition metal arene complexes, and are isolable intermidiates in the preparation of the trimpsi metal carbonyls. Unlike other known titanium(0) arene complexes, (trimpsi)Ti($\\eta\\sp6$-naphthalene) is paramagnetic. The X-ray crystal structure of (trimpsi)Ti($\\eta\\sp6$-naphthalene) shows a coordinated naphthalene ring that is warped at a dihedral angle of 12.4$\\sp\\circ$, whereas Ti(C$\\sb6$H$\\sb6$)$\\sb2$ and Ti(C$\\sb6$H$\\sb5$CH$\\sb3$)$\\sb2$ have planar arene rings, and the naphthalene ring in (trimpsi)V-($\\eta\\sp6$-naphthalene) has a dihedral angle of only 5.1$\\sp\\circ$. Like the group 4 carbonyls, (trimpsi)Ti($\\eta\\sp6$-naphthalene) exhibits exceptionally strong & back-bonding from the filled Ti 3d$\\sb{\\rm x}\\sp2\\sb{\\rm -y}\\sp2$ orbital to the naphthalene L.U.M.O. The ring warps such that the carbon atoms with the greatest L.U.M.O. coefficient have the shortest metal-carbon distances. In general, the greater the dihedral angle, the stronger the $\\delta$ back-bonding.","The 15-electron complexes (trimpsi)CrEt$\\sb3$ and (trimpsi)-CrBu$\\sp{\\rm n}\\sb3$ are thermally stable at room temperature, and undergo $\\beta$-elimination only at elevated temperatures. The $n$-butyl ligands in (trimpsi)CrBu$\\sp{\\rm n}\\sb3$ are structurally similar to those of $n$-butyl-main group compounds. These trialkylchromium(III) complexes are poor ethylene polymerization catalysts. The vanadium(III) alkyl (trimpsi)V(CH$\\sb2$SiMe$\\sb3$)Cl$\\sb2$ has also been prepared.","The chemistry of trimpsi organoyttrium complexes has also been briefly explored.","Made available in DSpace on 2011-05-07T14:00:02Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9010859.pdf: 5336417 bytes, checksum: ff9592561cd3fce6b904b1882b38e870 (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:01:46Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:29:19-05:00 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":["AAI9010859","(UMI)AAI9010859","http://hdl.handle.net/2142/23041"],"dc:language":["eng"],"dc:rights":["Copyright 1989 Gardner, Thomas George"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["\"Low-valent early transition metal complexes stabilized by the chelating tripod phosphine ligand ( t-butyl)tris((dimethylphosphino)methyl);silane (\"\"trimpsi\"\")\""],"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":"2026-07-22T22:25:21Z"}