{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70409"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70409","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Early Transition Metal Alkyl and Tetrahydroborate Complexes","abstract":"An investigation of early transition metal alkyl and tetrahydroborate complexes as catalytic models and ceramic precursors has been initiated. The compounds MX$\\sb2$ (dmpe)$\\sb2$, dmpe = 1,2-bis(dimethylphosphino)ethane, for M = Ti, V, Cr, and X = Br, I, BH$\\sb4$, have been prepared. These complexes are paramagnetic and have been shown by X-ray crystallography to have trans-octahedral structures. The BH$\\sb4\\sp{-}$ groups in Ti(BH$\\sb4)\\sb2$(dmpe)$\\sb2$ bond to the metal in a bidentate manner. This structure is in marked contrast to the structure of the vanadium analogue, V(BH$\\sb4)\\sb2$(dmpe)$\\sb2$, which displays two unidentate BH$\\sb4\\sp{-}$ groups.","abstract_html":"An investigation of early transition metal alkyl and tetrahydroborate complexes as catalytic models and ceramic precursors has been initiated. The compounds MX$\\sb2$ (dmpe)$\\sb2$, dmpe = 1,2-bis(dimethylphosphino)ethane, for M = Ti, V, Cr, and X = Br, I, BH$\\sb4$, have been prepared. These complexes are paramagnetic and have been shown by X-ray crystallography to have trans-octahedral structures. The BH$\\sb4\\sp{-}$ groups in Ti(BH$\\sb4)\\sb2$(dmpe)$\\sb2$ bond to the metal in a bidentate manner. This structure is in marked contrast to the structure of the vanadium analogue, V(BH$\\sb4)\\sb2$(dmpe)$\\sb2$, which displays two unidentate BH$\\sb4\\sp{-}$ groups.","abstract_has_math":true,"creators":["Jensen, James Allen"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Girolami, Gregory S."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:19:15Z","date_published":"2014-12-15T23:19:15Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic","Physics, Condensed Matter","Engineering, Materials Science"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8823157"],"render_values":[{"text":"(UMI)AAI8823157","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70409","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Girolami, Gregory S."]},{"key":"dc:creator","label":"Author","values":["Jensen, James Allen"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:19:15Z","10000-01-01","1988"]},{"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, Condensed Matter","Engineering, Materials Science"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8823157","http://hdl.handle.net/2142/70409"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["An investigation of early transition metal alkyl and tetrahydroborate complexes as catalytic models and ceramic precursors has been initiated. The compounds MX$\\sb2$ (dmpe)$\\sb2$, dmpe = 1,2-bis(dimethylphosphino)ethane, for M = Ti, V, Cr, and X = Br, I, BH$\\sb4$, have been prepared. These complexes are paramagnetic and have been shown by X-ray crystallography to have trans-octahedral structures. The BH$\\sb4\\sp{-}$ groups in Ti(BH$\\sb4)\\sb2$(dmpe)$\\sb2$ bond to the metal in a bidentate manner. This structure is in marked contrast to the structure of the vanadium analogue, V(BH$\\sb4)\\sb2$(dmpe)$\\sb2$, which displays two unidentate BH$\\sb4\\sp{-}$ groups.","Alkylation of Ti(BH$\\sb4)\\sb2$(dmpe)$\\sb2$ with LiMe results in the complex TiMe$\\sb2$(dmpe)$\\sb2$ which is diamagnetic in both solution and solid state. Single crystal X-ray and neutron diffraction studies show that there may be strong Ti-C $\\pi$-bonding. A tetragonal compression along the C-Ti-C bond vector accounts for the observed diamegnetism.","A series of complexes of the formula Ti(BH$\\sb4)\\sb3$(PR$\\sb3)\\sb2$ has been prepared where PR$\\sb3$ = PMe$\\sb3$, PEt$\\sb3$, PMe$\\sb3$Ph, and P(OMe)$\\sb3$. The X-ray crystal structure of Ti(BH$\\sb4)\\sb3$(PMe$\\sb3)\\sb2$ reveals a pseudo trigonal bipyramidal geometry in which two BH$\\sb4\\sp{-}$ groups display an unusual "side-on" bonding mode. The "side-on" ligation mode has been attributed to a Jahn-Teller distortion of the orbitally degenerate d$\\sp1$ ground state. In contrast, the non-Jahn-Teller susceptible vanadium analogue, V(BH$\\sb4)\\sb3$(PMe$\\sb3)\\sb2$, possesses a nearly ideal D$\\sb{\\rm 3h}$ geometry with three bidentate tetrahydroborate groups. Addition of excess PMe$\\sb3$ to V(BH$\\sb4)\\sb3$(PMe$\\sb3)\\sb2$ leads to the vanadium(II) hydride-bridged dimer (V(H)(BH$\\sb4$)(PMe$\\sb3)\\sb2\\rbrack\\sb2$, while addition of PMe$\\sb3$ and water forms the vanadium(III) oxo dimer (V(BH$\\sb4)\\sb2$(PMe$\\sb3)\\sb2\\rbrack\\sb2\\lbrack\\mu$-O) which has been structurally characterized.","The compound Ti(CH$\\sb2$CMe$\\sb3)\\sb4$ can be prepared by addition of Ti(OEt)$\\sb4$ to LiCH$\\sb2$CMe$\\sb3$. Sublimation of Ti(CH$\\sb2$CMe$\\sb3)\\sb4$ over a substrate heated to 250$\\sp\\circ$C results in the chemical vapor deposition of amorphous TiC thin films. This CVD approach has been extended to the Group 4 borides: Ti(BH$\\sb4)\\sb3$(MeOCH$\\sb2$CH$\\sb2$OMe) yields TiB$\\sb2$ at 200$\\sp\\circ$C, while Zr(BH$\\sb4)\\sb4$ and Hf(BH$\\sb4)\\sb4$ yield ZrB$\\sb2$ and HfB$\\sb2$ at 250$\\sp\\circ$C using the CVD process. The X-ray crystal structure of Ti(BH$\\sb4)\\sb3$(MeOCH$\\sb2$CH$\\sb2$OMe) is reported.","Made available in DSpace on 2014-12-15T23:19:15Z (GMT). No. of bitstreams: 1 8823157.pdf: 5914880 bytes, checksum: 2961c04e11880b5a9ed383bce22f767a (MD5) Previous issue date: 1988","Embargo set by: Seth Robbins for item 70575 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","198 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988."]},{"key":"dc:title","label":"Title","values":["Early Transition Metal Alkyl and Tetrahydroborate Complexes"]}]}],"canonical_facts":{"dc:contributor":["Girolami, Gregory S."],"dc:creator":["Jensen, James Allen"],"dc:date":["2014-12-15T23:19:15Z","10000-01-01","1988"],"dc:description":["An investigation of early transition metal alkyl and tetrahydroborate complexes as catalytic models and ceramic precursors has been initiated. The compounds MX$\\sb2$ (dmpe)$\\sb2$, dmpe = 1,2-bis(dimethylphosphino)ethane, for M = Ti, V, Cr, and X = Br, I, BH$\\sb4$, have been prepared. These complexes are paramagnetic and have been shown by X-ray crystallography to have trans-octahedral structures. The BH$\\sb4\\sp{-}$ groups in Ti(BH$\\sb4)\\sb2$(dmpe)$\\sb2$ bond to the metal in a bidentate manner. This structure is in marked contrast to the structure of the vanadium analogue, V(BH$\\sb4)\\sb2$(dmpe)$\\sb2$, which displays two unidentate BH$\\sb4\\sp{-}$ groups.","Alkylation of Ti(BH$\\sb4)\\sb2$(dmpe)$\\sb2$ with LiMe results in the complex TiMe$\\sb2$(dmpe)$\\sb2$ which is diamagnetic in both solution and solid state. Single crystal X-ray and neutron diffraction studies show that there may be strong Ti-C $\\pi$-bonding. A tetragonal compression along the C-Ti-C bond vector accounts for the observed diamegnetism.","A series of complexes of the formula Ti(BH$\\sb4)\\sb3$(PR$\\sb3)\\sb2$ has been prepared where PR$\\sb3$ = PMe$\\sb3$, PEt$\\sb3$, PMe$\\sb3$Ph, and P(OMe)$\\sb3$. The X-ray crystal structure of Ti(BH$\\sb4)\\sb3$(PMe$\\sb3)\\sb2$ reveals a pseudo trigonal bipyramidal geometry in which two BH$\\sb4\\sp{-}$ groups display an unusual "side-on" bonding mode. The "side-on" ligation mode has been attributed to a Jahn-Teller distortion of the orbitally degenerate d$\\sp1$ ground state. In contrast, the non-Jahn-Teller susceptible vanadium analogue, V(BH$\\sb4)\\sb3$(PMe$\\sb3)\\sb2$, possesses a nearly ideal D$\\sb{\\rm 3h}$ geometry with three bidentate tetrahydroborate groups. Addition of excess PMe$\\sb3$ to V(BH$\\sb4)\\sb3$(PMe$\\sb3)\\sb2$ leads to the vanadium(II) hydride-bridged dimer (V(H)(BH$\\sb4$)(PMe$\\sb3)\\sb2\\rbrack\\sb2$, while addition of PMe$\\sb3$ and water forms the vanadium(III) oxo dimer (V(BH$\\sb4)\\sb2$(PMe$\\sb3)\\sb2\\rbrack\\sb2\\lbrack\\mu$-O) which has been structurally characterized.","The compound Ti(CH$\\sb2$CMe$\\sb3)\\sb4$ can be prepared by addition of Ti(OEt)$\\sb4$ to LiCH$\\sb2$CMe$\\sb3$. Sublimation of Ti(CH$\\sb2$CMe$\\sb3)\\sb4$ over a substrate heated to 250$\\sp\\circ$C results in the chemical vapor deposition of amorphous TiC thin films. This CVD approach has been extended to the Group 4 borides: Ti(BH$\\sb4)\\sb3$(MeOCH$\\sb2$CH$\\sb2$OMe) yields TiB$\\sb2$ at 200$\\sp\\circ$C, while Zr(BH$\\sb4)\\sb4$ and Hf(BH$\\sb4)\\sb4$ yield ZrB$\\sb2$ and HfB$\\sb2$ at 250$\\sp\\circ$C using the CVD process. The X-ray crystal structure of Ti(BH$\\sb4)\\sb3$(MeOCH$\\sb2$CH$\\sb2$OMe) is reported.","Made available in DSpace on 2014-12-15T23:19:15Z (GMT). No. of bitstreams: 1 8823157.pdf: 5914880 bytes, checksum: 2961c04e11880b5a9ed383bce22f767a (MD5) Previous issue date: 1988","Embargo set by: Seth Robbins for item 70575 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","198 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988."],"dc:identifier":["(UMI)AAI8823157","http://hdl.handle.net/2142/70409"],"dc:subject":["Chemistry, Inorganic","Physics, Condensed Matter","Engineering, Materials Science"],"dc:title":["Early Transition Metal Alkyl and Tetrahydroborate Complexes"],"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":"2026-07-22T22:26:02Z"}