Organo-Ruthenium Supported Heteropolytungstates: Synthesis, Structure, Electrochemistry, and Oxidation Catalysis
The reaction of [Ru(arene)Cl2]2 (arene = benzene, p-cymene) with [X2W22O74(OH)2]12− (X = SbIII, BiIII) in buffer medium resulted in four organo-ruthenium supported heteropolytungstates, [Sb2W20O70(RuC6H6)2]10− (1), [Bi2W20O70(RuC6H6)2]10− (2), [Sb2W20O70(RuC10H14)2]10− (3), and [Bi2W20O70(RuC10H14)2...
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2009
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| Online Access: | http://hdl.handle.net/10725/17244 https://doi.org/10.1021/ic9009306 http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.php https://pubs.acs.org/doi/full/10.1021/ic9009306 |
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| author | Bi, Li-Hua |
| author2 | Al-Kadamany, Ghada Chubarova, Elena V. Dickman, Michael H. Chen, Lifang Gopala, Divakara S. Richards, Ryan M. Keita, Bineta Nadjo, Louis |
| author2_role | author author author author author author author author |
| author_facet | Bi, Li-Hua Al-Kadamany, Ghada Chubarova, Elena V. Dickman, Michael H. Chen, Lifang Gopala, Divakara S. Richards, Ryan M. Keita, Bineta Nadjo, Louis |
| author_role | author |
| dc.creator.none.fl_str_mv | Bi, Li-Hua Al-Kadamany, Ghada Chubarova, Elena V. Dickman, Michael H. Chen, Lifang Gopala, Divakara S. Richards, Ryan M. Keita, Bineta Nadjo, Louis |
| dc.date.none.fl_str_mv | 2009 2009-09-25 2025-09-11T08:49:07Z 2025-09-11T08:49:07Z |
| dc.identifier.none.fl_str_mv | 0020-1669 http://hdl.handle.net/10725/17244 https://doi.org/10.1021/ic9009306 Bi, L. H., Al-Kadamany, G., Chubarova, E. V., Dickman, M. H., Chen, L., Gopala, D. S., ... & Kortz, U. (2009). Organo-ruthenium supported heteropolytungstates: synthesis, structure, electrochemistry, and oxidation catalysis. Inorganic chemistry, 48(21), 10068-10077. http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.php https://pubs.acs.org/doi/full/10.1021/ic9009306 |
| dc.language.none.fl_str_mv | en |
| dc.relation.none.fl_str_mv | Inorganic Chemistry |
| dc.rights.*.fl_str_mv | info:eu-repo/semantics/openAccess |
| dc.title.none.fl_str_mv | Organo-Ruthenium Supported Heteropolytungstates: Synthesis, Structure, Electrochemistry, and Oxidation Catalysis |
| dc.type.none.fl_str_mv | Article info:eu-repo/semantics/publishedVersion info:eu-repo/semantics/article |
| description | The reaction of [Ru(arene)Cl2]2 (arene = benzene, p-cymene) with [X2W22O74(OH)2]12− (X = SbIII, BiIII) in buffer medium resulted in four organo-ruthenium supported heteropolytungstates, [Sb2W20O70(RuC6H6)2]10− (1), [Bi2W20O70(RuC6H6)2]10− (2), [Sb2W20O70(RuC10H14)2]10− (3), and [Bi2W20O70(RuC10H14)2]10− (4), which have been characterized in solution by multinuclear (183W, 13C, 1H) NMR, UV−vis spectroscopy, electrochemistry, and in the solid state by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and elemental analysis. Polyanions 1, 2, and 4 crystallize in the triclinic system, space group P1̅ with the following unit cell parameters: K5Na5[Sb2W20O70(RuC6H6)2]·22H2O (KNa-1), a = 12.1625(2) Å, b = 13.1677(2) Å, c = 16.0141(3) Å, α = 78.9201(7)°, β = 74.4442(8)°, γ = 78.9019(8)°, and Z = 1; Cs2Na8[Bi2W20O70(RuC6H6)2]·30H2O (CsNa-2), a = 11.6353(7) Å, b = 13.3638(7) Å, c = 16.7067(8) Å, α = 79.568(2)°, β = 71.103(2)°, γ = 80.331(2)°, and Z = 1; Na10[Bi2W20O70(RuC10H14)2]·35H2O (Na-4), a = 15.7376(12) Å, b = 15.9806(13) Å, c = 24.2909(19) Å, α = 92.109(4)°, β = 101.354(4)°, γ = 97.365(3)°, and Z = 2. Polyanions 1−4 consist of two (L)Ru2+ (L = benzene or p-cymene) units linked to a [X2W20O70]14− (X = SbIII, BiIII) fragment via Ru−O(W) bonds resulting in an assembly with idealized C2h symmetry. Polyanions 1−4 are stable in solution as indicated by the expected 183W, 13C, and 1H NMR spectra. The electrochemistry of 1−4 is described by considering the reduction and the oxidation processes. The nature of the arene in Ru(arene) has practically no influence on the formal potentials of the W-centers, which are more sensitive to the Sb or Bi hetero atoms. The results suggest that the respective Sb- and Bi derivatives have very different pKa values, with the reduced form of 1 being the most basic, thus permitting the observation of two well-developed voltammetric waves at pH 6. In contrast, the identity of the arene influences the oxidation processes, thus permitting to distinguish them. A strong electrocatalytic water oxidation peak is observed that is more positive than the one corresponding to the Ru(arene) oxidation process. Also a stepwise oxidation of the Ru(benzene) group could be observed at pH 3. The catalytic efficiency, on the other hand, of 1−4 toward the oxidation of n-hexadecane and p-xylene illustrated the effect of ruthenium substitution on the polyanion catalytic performance. |
| eu_rights_str_mv | openAccess |
| format | article |
| id | LAURepo_d3df9f28ebe82d6cfde9c679e2f0dee0 |
| identifier_str_mv | 0020-1669 Bi, L. H., Al-Kadamany, G., Chubarova, E. V., Dickman, M. H., Chen, L., Gopala, D. S., ... & Kortz, U. (2009). Organo-ruthenium supported heteropolytungstates: synthesis, structure, electrochemistry, and oxidation catalysis. Inorganic chemistry, 48(21), 10068-10077. |
| language_invalid_str_mv | en |
| network_acronym_str | LAURepo |
| network_name_str | Lebanese American University repository |
| oai_identifier_str | oai:laur.lau.edu.lb:10725/17244 |
| publishDate | 2009 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| spelling | Organo-Ruthenium Supported Heteropolytungstates: Synthesis, Structure, Electrochemistry, and Oxidation CatalysisBi, Li-HuaAl-Kadamany, GhadaChubarova, Elena V.Dickman, Michael H.Chen, LifangGopala, Divakara S.Richards, Ryan M.Keita, BinetaNadjo, LouisThe reaction of [Ru(arene)Cl2]2 (arene = benzene, p-cymene) with [X2W22O74(OH)2]12− (X = SbIII, BiIII) in buffer medium resulted in four organo-ruthenium supported heteropolytungstates, [Sb2W20O70(RuC6H6)2]10− (1), [Bi2W20O70(RuC6H6)2]10− (2), [Sb2W20O70(RuC10H14)2]10− (3), and [Bi2W20O70(RuC10H14)2]10− (4), which have been characterized in solution by multinuclear (183W, 13C, 1H) NMR, UV−vis spectroscopy, electrochemistry, and in the solid state by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and elemental analysis. Polyanions 1, 2, and 4 crystallize in the triclinic system, space group P1̅ with the following unit cell parameters: K5Na5[Sb2W20O70(RuC6H6)2]·22H2O (KNa-1), a = 12.1625(2) Å, b = 13.1677(2) Å, c = 16.0141(3) Å, α = 78.9201(7)°, β = 74.4442(8)°, γ = 78.9019(8)°, and Z = 1; Cs2Na8[Bi2W20O70(RuC6H6)2]·30H2O (CsNa-2), a = 11.6353(7) Å, b = 13.3638(7) Å, c = 16.7067(8) Å, α = 79.568(2)°, β = 71.103(2)°, γ = 80.331(2)°, and Z = 1; Na10[Bi2W20O70(RuC10H14)2]·35H2O (Na-4), a = 15.7376(12) Å, b = 15.9806(13) Å, c = 24.2909(19) Å, α = 92.109(4)°, β = 101.354(4)°, γ = 97.365(3)°, and Z = 2. Polyanions 1−4 consist of two (L)Ru2+ (L = benzene or p-cymene) units linked to a [X2W20O70]14− (X = SbIII, BiIII) fragment via Ru−O(W) bonds resulting in an assembly with idealized C2h symmetry. Polyanions 1−4 are stable in solution as indicated by the expected 183W, 13C, and 1H NMR spectra. The electrochemistry of 1−4 is described by considering the reduction and the oxidation processes. The nature of the arene in Ru(arene) has practically no influence on the formal potentials of the W-centers, which are more sensitive to the Sb or Bi hetero atoms. The results suggest that the respective Sb- and Bi derivatives have very different pKa values, with the reduced form of 1 being the most basic, thus permitting the observation of two well-developed voltammetric waves at pH 6. In contrast, the identity of the arene influences the oxidation processes, thus permitting to distinguish them. A strong electrocatalytic water oxidation peak is observed that is more positive than the one corresponding to the Ru(arene) oxidation process. Also a stepwise oxidation of the Ru(benzene) group could be observed at pH 3. The catalytic efficiency, on the other hand, of 1−4 toward the oxidation of n-hexadecane and p-xylene illustrated the effect of ruthenium substitution on the polyanion catalytic performance.Published2025-09-11T08:49:07Z2025-09-11T08:49:07Z20092009-09-25Articleinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article0020-1669http://hdl.handle.net/10725/17244https://doi.org/10.1021/ic9009306Bi, L. H., Al-Kadamany, G., Chubarova, E. V., Dickman, M. H., Chen, L., Gopala, D. S., ... & Kortz, U. (2009). Organo-ruthenium supported heteropolytungstates: synthesis, structure, electrochemistry, and oxidation catalysis. Inorganic chemistry, 48(21), 10068-10077.http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.phphttps://pubs.acs.org/doi/full/10.1021/ic9009306enInorganic Chemistryinfo:eu-repo/semantics/openAccessoai:laur.lau.edu.lb:10725/172442025-10-23T14:11:51Z |
| spellingShingle | Organo-Ruthenium Supported Heteropolytungstates: Synthesis, Structure, Electrochemistry, and Oxidation Catalysis Bi, Li-Hua |
| status_str | publishedVersion |
| title | Organo-Ruthenium Supported Heteropolytungstates: Synthesis, Structure, Electrochemistry, and Oxidation Catalysis |
| title_full | Organo-Ruthenium Supported Heteropolytungstates: Synthesis, Structure, Electrochemistry, and Oxidation Catalysis |
| title_fullStr | Organo-Ruthenium Supported Heteropolytungstates: Synthesis, Structure, Electrochemistry, and Oxidation Catalysis |
| title_full_unstemmed | Organo-Ruthenium Supported Heteropolytungstates: Synthesis, Structure, Electrochemistry, and Oxidation Catalysis |
| title_short | Organo-Ruthenium Supported Heteropolytungstates: Synthesis, Structure, Electrochemistry, and Oxidation Catalysis |
| title_sort | Organo-Ruthenium Supported Heteropolytungstates: Synthesis, Structure, Electrochemistry, and Oxidation Catalysis |
| url | http://hdl.handle.net/10725/17244 https://doi.org/10.1021/ic9009306 http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.php https://pubs.acs.org/doi/full/10.1021/ic9009306 |