{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/102800"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/102800","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Low-temperature protonation studies of an electron-poor osmium methyl complex, and molecular precursors for the construction of graphene nanostructues with atomically precise edge structures","abstract":"Treatment of Cl2PCH2Cl2 with CF3SiMe3 in the presence of CsF promotor gave the cesium salt Cs[((CF3)2P)2CH], which was converted to the electron-poor diphosphine (CF3)2PCH2P(CF3)2 (dfmpm) by addition of ethereal hydrogen chloride. Treatment of (C5Me5)2Os2Br4 with excess dfmpm in the presence of zinc dust in refluxing ethanol gave the piano stool osmium complex (C5Me5)Os(dfmpm)Br, which was converted to (C5Me5)Os(dfmpm)Me in excellent yield by treatment with excess ZnMe2 in refluxing toluene. The analogous ethyl complex (C5Me5)Os(dfmpm)Et can also be prepared in a similar fashion, but with simultaneous formation of the hydrides (C5Me5)Os(dfmpm)H and (C5Me5)Os(kappa-1-dfmpm)(C2H4)H by beta-hydrogen elimination. Protonation of (C5Me5)Os(dfmpm)Me with (CF3SO2)2NH at –110 °C in CDCl2F yielded the methane coordination complex [(C5Me5)Os(dfmpm)CH4][N(SO2CF3)2]. The analogous 13CH4 complex exhibited a binomial quintet in the 13C NMR with a coupling constant (127 Hz) almost identical to that of free methane (125 Hz). Kinetic analysis revealed that the enthalpy and entropy of activation for methane loss was ΔH‡ = 14.9 ± 1.5 kcal mol-1 and ΔS‡ = 12.3 ± 8.8 cal mol-1 K-1, respectively, and the barrier for methane loss was ΔG‡ = 12.8 ± 0.1 kcal/mol at –100 °C, which is in good agreement with previous DFT calculations. Treatment of (C5Me5)Os(dfmpm)13CH3 and (C5Me5)Os(dfmpm)13CHD2 with (CF3SO2)2NH and (CF3SO2)2ND at –110 °C in CDCl2F gave a mixture of the four methane complex isotopologs [(C5Me5)Os(dfmpm)13CH4][N(SO2CF3)2], [(C5Me5)Os(dfmpm)13CH3D][N(SO2CF3)2], [(C5Me5)Os(dfmpm)13CH2D2][N(SO2CF3)2], and [(C5Me5)Os(dfmpm)13CHD3][N(SO2CF3)2] in one NMR tube, which permitted an isotopic perturbation of resonance (IPR) analysis. The IPR data in conjunction with the DFT analysis indicated that methane is coordinated to osmium in a kappa-1 fashion. A reinvestigation of the protonation of the ruthenium complex (C5Me5)Os(dmpm)Me resulted in rapid generation of free methane, even at low temperature. Several oligophenylene derivatives were investigated as possible precursors for the surface-assisted synthesis of various graphene structures, including graphene sheets, graphene sheets with a regular pattern of holes, and graphene nanoribbons (GNRs). Criteria were specified for determining the likelihood that oligophenylene precursors would form the intended structures. Through this approach, 2,6-bis(2,5-dibromophenyl)biphenyl and 1,4-bis(2,6-dibromophenyl)benzene were identified as attractive candidates for the surface-assisted construction of graphene structures. Solution-based iterative cross-coupling (ICC) of anthracene derivatives was also investigated as an alternative strategy for the construction of GNRs. Synthetic routes and general fabrication methods that could lead to the construction of GNR-based electronic structures were suggested. In initial attempts to synthesize the identified GNR precursor candidates, Suzuki coupling of 2,2′-diiodobiphenyl with (2,5-dibromophenyl)boronic acid failed to yield the desired 2,6-bis(2,5-dibromophenyl)biphenyl product. On the other hand, 1,4-bis(2,6-dibromophenyl)benzene was successfully prepared, although in low yield, by Suzuki coupling of 1,4-phenylenediboronic acid with 1,3-dibromo-2-iodobenzene; the latter compound was synthesized by treatment of 1,3-dibromobenzene with LDA, followed by addition of iodine.","abstract_html":"Treatment of Cl2PCH2Cl2 with CF3SiMe3 in the presence of CsF promotor gave the cesium salt Cs[((CF3)2P)2CH], which was converted to the electron-poor diphosphine (CF3)2PCH2P(CF3)2 (dfmpm) by addition of ethereal hydrogen chloride. Treatment of (C5Me5)2Os2Br4 with excess dfmpm in the presence of zinc dust in refluxing ethanol gave the piano stool osmium complex (C5Me5)Os(dfmpm)Br, which was converted to (C5Me5)Os(dfmpm)Me in excellent yield by treatment with excess ZnMe2 in refluxing toluene. The analogous ethyl complex (C5Me5)Os(dfmpm)Et can also be prepared in a similar fashion, but with simultaneous formation of the hydrides (C5Me5)Os(dfmpm)H and (C5Me5)Os(kappa-1-dfmpm)(C2H4)H by beta-hydrogen elimination. Protonation of (C5Me5)Os(dfmpm)Me with (CF3SO2)2NH at –110 °C in CDCl2F yielded the methane coordination complex [(C5Me5)Os(dfmpm)CH4][N(SO2CF3)2]. The analogous 13CH4 complex exhibited a binomial quintet in the 13C NMR with a coupling constant (127 Hz) almost identical to that of free methane (125 Hz). Kinetic analysis revealed that the enthalpy and entropy of activation for methane loss was ΔH‡ = 14.9 ± 1.5 kcal mol-1 and ΔS‡ = 12.3 ± 8.8 cal mol-1 K-1, respectively, and the barrier for methane loss was ΔG‡ = 12.8 ± 0.1 kcal/mol at –100 °C, which is in good agreement with previous DFT calculations. Treatment of (C5Me5)Os(dfmpm)13CH3 and (C5Me5)Os(dfmpm)13CHD2 with (CF3SO2)2NH and (CF3SO2)2ND at –110 °C in CDCl2F gave a mixture of the four methane complex isotopologs [(C5Me5)Os(dfmpm)13CH4][N(SO2CF3)2], [(C5Me5)Os(dfmpm)13CH3D][N(SO2CF3)2], [(C5Me5)Os(dfmpm)13CH2D2][N(SO2CF3)2], and [(C5Me5)Os(dfmpm)13CHD3][N(SO2CF3)2] in one NMR tube, which permitted an isotopic perturbation of resonance (IPR) analysis. The IPR data in conjunction with the DFT analysis indicated that methane is coordinated to osmium in a kappa-1 fashion. A reinvestigation of the protonation of the ruthenium complex (C5Me5)Os(dmpm)Me resulted in rapid generation of free methane, even at low temperature. Several oligophenylene derivatives were investigated as possible precursors for the surface-assisted synthesis of various graphene structures, including graphene sheets, graphene sheets with a regular pattern of holes, and graphene nanoribbons (GNRs). Criteria were specified for determining the likelihood that oligophenylene precursors would form the intended structures. Through this approach, 2,6-bis(2,5-dibromophenyl)biphenyl and 1,4-bis(2,6-dibromophenyl)benzene were identified as attractive candidates for the surface-assisted construction of graphene structures. Solution-based iterative cross-coupling (ICC) of anthracene derivatives was also investigated as an alternative strategy for the construction of GNRs. Synthetic routes and general fabrication methods that could lead to the construction of GNR-based electronic structures were suggested. In initial attempts to synthesize the identified GNR precursor candidates, Suzuki coupling of 2,2′-diiodobiphenyl with (2,5-dibromophenyl)boronic acid failed to yield the desired 2,6-bis(2,5-dibromophenyl)biphenyl product. On the other hand, 1,4-bis(2,6-dibromophenyl)benzene was successfully prepared, although in low yield, by Suzuki coupling of 1,4-phenylenediboronic acid with 1,3-dibromo-2-iodobenzene; the latter compound was synthesized by treatment of 1,3-dibromobenzene with LDA, followed by addition of iodine.","abstract_has_math":false,"creators":["Sempsrott, Peter J."],"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.","Lyding, Joseph W.","Murphy, Catherine J.","Rauchfuss, Thomas B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2019,"date_issued":"2019-02-07T20:35:59Z","date_published":"2019-02-07T20:35:59Z","updated_at":"2026-07-22T22:24:42Z","subjects":["Methane activation","osmium methyl complex","diphosphine","NMR spectroscopy","polyarene","graphene nanostructures"],"languages":["en"],"rights":["Copyright 2018 Peter J. Sempsrott"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/102800","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Girolami, Gregory S.","Lyding, Joseph W.","Murphy, Catherine J.","Rauchfuss, Thomas B."]},{"key":"dc:creator","label":"Author","values":["Sempsrott, Peter J."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2019-02-07T20:35:59Z","2021-02-08T10:15:39Z","2018-11-28","2018-12"]},{"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":["Methane activation","osmium methyl complex","diphosphine","NMR spectroscopy","polyarene","graphene nanostructures"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2018 Peter J. Sempsrott"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/102800"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Treatment of Cl2PCH2Cl2 with CF3SiMe3 in the presence of CsF promotor gave the cesium salt Cs[((CF3)2P)2CH], which was converted to the electron-poor diphosphine (CF3)2PCH2P(CF3)2 (dfmpm) by addition of ethereal hydrogen chloride. Treatment of (C5Me5)2Os2Br4 with excess dfmpm in the presence of zinc dust in refluxing ethanol gave the piano stool osmium complex (C5Me5)Os(dfmpm)Br, which was converted to (C5Me5)Os(dfmpm)Me in excellent yield by treatment with excess ZnMe2 in refluxing toluene. The analogous ethyl complex (C5Me5)Os(dfmpm)Et can also be prepared in a similar fashion, but with simultaneous formation of the hydrides (C5Me5)Os(dfmpm)H and (C5Me5)Os(kappa-1-dfmpm)(C2H4)H by beta-hydrogen elimination. Protonation of (C5Me5)Os(dfmpm)Me with (CF3SO2)2NH at –110 °C in CDCl2F yielded the methane coordination complex [(C5Me5)Os(dfmpm)CH4][N(SO2CF3)2]. The analogous 13CH4 complex exhibited a binomial quintet in the 13C NMR with a coupling constant (127 Hz) almost identical to that of free methane (125 Hz). Kinetic analysis revealed that the enthalpy and entropy of activation for methane loss was ΔH‡ = 14.9 ± 1.5 kcal mol-1 and ΔS‡ = 12.3 ± 8.8 cal mol-1 K-1, respectively, and the barrier for methane loss was ΔG‡ = 12.8 ± 0.1 kcal/mol at –100 °C, which is in good agreement with previous DFT calculations. Treatment of (C5Me5)Os(dfmpm)13CH3 and (C5Me5)Os(dfmpm)13CHD2 with (CF3SO2)2NH and (CF3SO2)2ND at –110 °C in CDCl2F gave a mixture of the four methane complex isotopologs [(C5Me5)Os(dfmpm)13CH4][N(SO2CF3)2], [(C5Me5)Os(dfmpm)13CH3D][N(SO2CF3)2], [(C5Me5)Os(dfmpm)13CH2D2][N(SO2CF3)2], and [(C5Me5)Os(dfmpm)13CHD3][N(SO2CF3)2] in one NMR tube, which permitted an isotopic perturbation of resonance (IPR) analysis. The IPR data in conjunction with the DFT analysis indicated that methane is coordinated to osmium in a kappa-1 fashion. A reinvestigation of the protonation of the ruthenium complex (C5Me5)Os(dmpm)Me resulted in rapid generation of free methane, even at low temperature. Several oligophenylene derivatives were investigated as possible precursors for the surface-assisted synthesis of various graphene structures, including graphene sheets, graphene sheets with a regular pattern of holes, and graphene nanoribbons (GNRs). Criteria were specified for determining the likelihood that oligophenylene precursors would form the intended structures. Through this approach, 2,6-bis(2,5-dibromophenyl)biphenyl and 1,4-bis(2,6-dibromophenyl)benzene were identified as attractive candidates for the surface-assisted construction of graphene structures. Solution-based iterative cross-coupling (ICC) of anthracene derivatives was also investigated as an alternative strategy for the construction of GNRs. Synthetic routes and general fabrication methods that could lead to the construction of GNR-based electronic structures were suggested. In initial attempts to synthesize the identified GNR precursor candidates, Suzuki coupling of 2,2′-diiodobiphenyl with (2,5-dibromophenyl)boronic acid failed to yield the desired 2,6-bis(2,5-dibromophenyl)biphenyl product. On the other hand, 1,4-bis(2,6-dibromophenyl)benzene was successfully prepared, although in low yield, by Suzuki coupling of 1,4-phenylenediboronic acid with 1,3-dibromo-2-iodobenzene; the latter compound was synthesized by treatment of 1,3-dibromobenzene with LDA, followed by addition of iodine.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2020-12-01","The student, Peter Sempsrott, accepted the attached license on 2018-11-26 at 13:23.","The student, Peter Sempsrott, submitted this Dissertation for approval on 2018-11-26 at 13:57.","This Dissertation was approved for publication on 2018-11-28 at 12:02.","DSpace SAF Submission Ingestion Package generated from Vireo submission #13102 on 2019-02-07 at 14:17:51","Made available in DSpace on 2019-02-07T20:35:59Z (GMT). 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Treatment of (C5Me5)2Os2Br4 with excess dfmpm in the presence of zinc dust in refluxing ethanol gave the piano stool osmium complex (C5Me5)Os(dfmpm)Br, which was converted to (C5Me5)Os(dfmpm)Me in excellent yield by treatment with excess ZnMe2 in refluxing toluene. The analogous ethyl complex (C5Me5)Os(dfmpm)Et can also be prepared in a similar fashion, but with simultaneous formation of the hydrides (C5Me5)Os(dfmpm)H and (C5Me5)Os(kappa-1-dfmpm)(C2H4)H by beta-hydrogen elimination. Protonation of (C5Me5)Os(dfmpm)Me with (CF3SO2)2NH at –110 °C in CDCl2F yielded the methane coordination complex [(C5Me5)Os(dfmpm)CH4][N(SO2CF3)2]. The analogous 13CH4 complex exhibited a binomial quintet in the 13C NMR with a coupling constant (127 Hz) almost identical to that of free methane (125 Hz). Kinetic analysis revealed that the enthalpy and entropy of activation for methane loss was ΔH‡ = 14.9 ± 1.5 kcal mol-1 and ΔS‡ = 12.3 ± 8.8 cal mol-1 K-1, respectively, and the barrier for methane loss was ΔG‡ = 12.8 ± 0.1 kcal/mol at –100 °C, which is in good agreement with previous DFT calculations. Treatment of (C5Me5)Os(dfmpm)13CH3 and (C5Me5)Os(dfmpm)13CHD2 with (CF3SO2)2NH and (CF3SO2)2ND at –110 °C in CDCl2F gave a mixture of the four methane complex isotopologs [(C5Me5)Os(dfmpm)13CH4][N(SO2CF3)2], [(C5Me5)Os(dfmpm)13CH3D][N(SO2CF3)2], [(C5Me5)Os(dfmpm)13CH2D2][N(SO2CF3)2], and [(C5Me5)Os(dfmpm)13CHD3][N(SO2CF3)2] in one NMR tube, which permitted an isotopic perturbation of resonance (IPR) analysis. The IPR data in conjunction with the DFT analysis indicated that methane is coordinated to osmium in a kappa-1 fashion. A reinvestigation of the protonation of the ruthenium complex (C5Me5)Os(dmpm)Me resulted in rapid generation of free methane, even at low temperature. Several oligophenylene derivatives were investigated as possible precursors for the surface-assisted synthesis of various graphene structures, including graphene sheets, graphene sheets with a regular pattern of holes, and graphene nanoribbons (GNRs). Criteria were specified for determining the likelihood that oligophenylene precursors would form the intended structures. Through this approach, 2,6-bis(2,5-dibromophenyl)biphenyl and 1,4-bis(2,6-dibromophenyl)benzene were identified as attractive candidates for the surface-assisted construction of graphene structures. Solution-based iterative cross-coupling (ICC) of anthracene derivatives was also investigated as an alternative strategy for the construction of GNRs. Synthetic routes and general fabrication methods that could lead to the construction of GNR-based electronic structures were suggested. In initial attempts to synthesize the identified GNR precursor candidates, Suzuki coupling of 2,2′-diiodobiphenyl with (2,5-dibromophenyl)boronic acid failed to yield the desired 2,6-bis(2,5-dibromophenyl)biphenyl product. On the other hand, 1,4-bis(2,6-dibromophenyl)benzene was successfully prepared, although in low yield, by Suzuki coupling of 1,4-phenylenediboronic acid with 1,3-dibromo-2-iodobenzene; the latter compound was synthesized by treatment of 1,3-dibromobenzene with LDA, followed by addition of iodine.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2020-12-01","The student, Peter Sempsrott, accepted the attached license on 2018-11-26 at 13:23.","The student, Peter Sempsrott, submitted this Dissertation for approval on 2018-11-26 at 13:57.","This Dissertation was approved for publication on 2018-11-28 at 12:02.","DSpace SAF Submission Ingestion Package generated from Vireo submission #13102 on 2019-02-07 at 14:17:51","Made available in DSpace on 2019-02-07T20:35:59Z (GMT). No. of bitstreams: 3 SEMPSROTT-DISSERTATION-2018.pdf: 5305527 bytes, checksum: 4f6334beb539bcf0c5fc70fb6113ff82 (MD5) LICENSE.txt: 4212 bytes, checksum: 3973ed135678d4e5e51dfa1c0d416b6c (MD5) PROQUEST_LICENSE.txt: 4558 bytes, checksum: b0619f34b9877a5ae7ec23b2cd9d916a (MD5) Previous issue date: 2018-11-28","Embargo set by: Seth Robbins for item 109824 Lift date: 2021-02-07T20:36:09Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 109824 Lift date: 2021-02-07T20:39:46Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 109824 Lift date: 2021-02-07T20:44:35Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","U of I Only Restriction Lifted for Item 109824 on 2021-02-08T10:15:39Z."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/2142/102800"],"dc:language":["en"],"dc:rights":["Copyright 2018 Peter J. Sempsrott"],"dc:subject":["Methane activation","osmium methyl complex","diphosphine","NMR spectroscopy","polyarene","graphene nanostructures"],"dc:title":["Low-temperature protonation studies of an electron-poor osmium methyl complex, and molecular precursors for the construction of graphene nanostructues with atomically precise edge structures"],"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":"2026-07-22T22:24:42Z"}