Facile synthesis of mononuclear early transition-metal complexes of κ[superscript 3]cyclo-tetrametaphosphate ([P[subscript 4]O[subscript 12]][superscript 4−]) and cyclo-trimetaphosphate ([P[subscript 3]O[subscript 9]][superscript 3−])
We herein report the preparation of several mononuclear-metaphosphate complexes using simple techniques and mild conditions with yields ranging from 56% to 78%. Treatment of cyclo-tetrametaphosphate ([TBA]4[P4O12]·5H2O, TBA = tetra-n-butylammonium) with various metal sources including (CH3CN)3Mo(CO)...
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| Format: | Article |
| Language: | en_US |
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Royal Society of Chemistry
2014
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| Online Access: | http://hdl.handle.net/1721.1/90949 https://orcid.org/0000-0003-2568-3269 |
| _version_ | 1811071527067582464 |
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| author | Manna, Cesar M. Nassar, Mostafa Y. Tofan, Daniel Chakarawet, Khetpakorn Cummins, Christopher C. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Manna, Cesar M. Nassar, Mostafa Y. Tofan, Daniel Chakarawet, Khetpakorn Cummins, Christopher C. |
| author_sort | Manna, Cesar M. |
| collection | MIT |
| description | We herein report the preparation of several mononuclear-metaphosphate complexes using simple techniques and mild conditions with yields ranging from 56% to 78%. Treatment of cyclo-tetrametaphosphate ([TBA]4[P4O12]·5H2O, TBA = tetra-n-butylammonium) with various metal sources including (CH3CN)3Mo(CO)3, (CH3CN)2Mo(CO)2(η3-C3H5)Cl, MoO2Cl2(OSMe2)2, and VOF3, leads to the clean and rapid formation of [TBA]4[(P4O12)Mo(CO)3]·2H2O, [TBA]3[(P4O12)Mo(CO)2(η3-C3H5)], [TBA]3[(P4O12)MoO2Cl] and [TBA]3[(P4O12)VOF2]·Et2O salts in isolated yields of 69, 56, 68, and 56% respectively. NMR spectroscopy, NMR simulations and single crystal X-ray studies reveal that the [P4O12]4− anion behaves as a tridentate ligand wherein one of the metaphosphate groups is not directly bound to the metal. cyclo-Trimetaphosphate-metal complexes were prepared using a similar procedure i.e., treatment of [PPN]3[P3O9]·H2O (PPN = bis(triphenylphosphine)iminium) with the metal sources (CH3CN)2Mo(CO)2(η3-C3H5)Cl, MoO2Cl2(OSMe2)2, MoOCl3, VOF3, WOCl4, and WO2Cl2(CH3CN)2 to produce the corresponding salts, [PPN]2[(P3O9)Mo(CO)2(η3-C3H5)], [PPN]2[(P3O9)MoO2Cl], [PPN]2[(P3O9)MoOCl2], [PPN]2[(P3O9)VOF2]·2CH2Cl2, and [PPN]2[(P3O9)WO2Cl] in isolated yields of 78, 56, 75, 59, and 77% respectively. NMR spectroscopy, NMR simulations and single-crystal X-ray studies indicate that the trianionic ligand [P3O9]3− in these complexes also has κ3 connectivity. |
| first_indexed | 2024-09-23T08:52:35Z |
| format | Article |
| id | mit-1721.1/90949 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T08:52:35Z |
| publishDate | 2014 |
| publisher | Royal Society of Chemistry |
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| spelling | mit-1721.1/909492022-09-26T08:53:26Z Facile synthesis of mononuclear early transition-metal complexes of κ[superscript 3]cyclo-tetrametaphosphate ([P[subscript 4]O[subscript 12]][superscript 4−]) and cyclo-trimetaphosphate ([P[subscript 3]O[subscript 9]][superscript 3−]) Facile synthesis of mononuclear early transition-metal complexes of κ3cyclo-tetrametaphosphate ([P4O12]4−) and cyclo-trimetaphosphate ([P3O9]3−) Manna, Cesar M. Nassar, Mostafa Y. Tofan, Daniel Chakarawet, Khetpakorn Cummins, Christopher C. Massachusetts Institute of Technology. Department of Chemistry Manna, Cesar M. Nassar, Mostafa Y. Tofan, Daniel Chakarawet, Khetpakorn Cummins, Christopher C. We herein report the preparation of several mononuclear-metaphosphate complexes using simple techniques and mild conditions with yields ranging from 56% to 78%. Treatment of cyclo-tetrametaphosphate ([TBA]4[P4O12]·5H2O, TBA = tetra-n-butylammonium) with various metal sources including (CH3CN)3Mo(CO)3, (CH3CN)2Mo(CO)2(η3-C3H5)Cl, MoO2Cl2(OSMe2)2, and VOF3, leads to the clean and rapid formation of [TBA]4[(P4O12)Mo(CO)3]·2H2O, [TBA]3[(P4O12)Mo(CO)2(η3-C3H5)], [TBA]3[(P4O12)MoO2Cl] and [TBA]3[(P4O12)VOF2]·Et2O salts in isolated yields of 69, 56, 68, and 56% respectively. NMR spectroscopy, NMR simulations and single crystal X-ray studies reveal that the [P4O12]4− anion behaves as a tridentate ligand wherein one of the metaphosphate groups is not directly bound to the metal. cyclo-Trimetaphosphate-metal complexes were prepared using a similar procedure i.e., treatment of [PPN]3[P3O9]·H2O (PPN = bis(triphenylphosphine)iminium) with the metal sources (CH3CN)2Mo(CO)2(η3-C3H5)Cl, MoO2Cl2(OSMe2)2, MoOCl3, VOF3, WOCl4, and WO2Cl2(CH3CN)2 to produce the corresponding salts, [PPN]2[(P3O9)Mo(CO)2(η3-C3H5)], [PPN]2[(P3O9)MoO2Cl], [PPN]2[(P3O9)MoOCl2], [PPN]2[(P3O9)VOF2]·2CH2Cl2, and [PPN]2[(P3O9)WO2Cl] in isolated yields of 78, 56, 75, 59, and 77% respectively. NMR spectroscopy, NMR simulations and single-crystal X-ray studies indicate that the trianionic ligand [P3O9]3− in these complexes also has κ3 connectivity. Eni S.p.A. (Firm) Eni-MIT Solar Frontiers Center (Program) 2014-10-15T19:07:40Z 2014-10-15T19:07:40Z 2014 Article http://purl.org/eprint/type/JournalArticle 1477-9226 1477-9234 http://hdl.handle.net/1721.1/90949 Manna, Cesar M., Mostafa Y. Nassar, Daniel Tofan, Khetpakorn Chakarawet, and Christopher C. Cummins. “Facile Synthesis of Mononuclear Early Transition-Metal Complexes of Κ3cyclo-Tetrametaphosphate ([P4O12]4−) and Cyclo-Trimetaphosphate ([P3O9]3−).” Dalton Transactions 43, no. 4 (2013): 1509. https://orcid.org/0000-0003-2568-3269 en_US http://dx.doi.org/10.1039/c3dt52526k Dalton Transactions Creative Commons Attribution http://creativecommons.org/licenses/by/3.0/ application/pdf Royal Society of Chemistry RSC |
| spellingShingle | Manna, Cesar M. Nassar, Mostafa Y. Tofan, Daniel Chakarawet, Khetpakorn Cummins, Christopher C. Facile synthesis of mononuclear early transition-metal complexes of κ[superscript 3]cyclo-tetrametaphosphate ([P[subscript 4]O[subscript 12]][superscript 4−]) and cyclo-trimetaphosphate ([P[subscript 3]O[subscript 9]][superscript 3−]) |
| title | Facile synthesis of mononuclear early transition-metal complexes of κ[superscript 3]cyclo-tetrametaphosphate ([P[subscript 4]O[subscript 12]][superscript 4−]) and cyclo-trimetaphosphate ([P[subscript 3]O[subscript 9]][superscript 3−]) |
| title_full | Facile synthesis of mononuclear early transition-metal complexes of κ[superscript 3]cyclo-tetrametaphosphate ([P[subscript 4]O[subscript 12]][superscript 4−]) and cyclo-trimetaphosphate ([P[subscript 3]O[subscript 9]][superscript 3−]) |
| title_fullStr | Facile synthesis of mononuclear early transition-metal complexes of κ[superscript 3]cyclo-tetrametaphosphate ([P[subscript 4]O[subscript 12]][superscript 4−]) and cyclo-trimetaphosphate ([P[subscript 3]O[subscript 9]][superscript 3−]) |
| title_full_unstemmed | Facile synthesis of mononuclear early transition-metal complexes of κ[superscript 3]cyclo-tetrametaphosphate ([P[subscript 4]O[subscript 12]][superscript 4−]) and cyclo-trimetaphosphate ([P[subscript 3]O[subscript 9]][superscript 3−]) |
| title_short | Facile synthesis of mononuclear early transition-metal complexes of κ[superscript 3]cyclo-tetrametaphosphate ([P[subscript 4]O[subscript 12]][superscript 4−]) and cyclo-trimetaphosphate ([P[subscript 3]O[subscript 9]][superscript 3−]) |
| title_sort | facile synthesis of mononuclear early transition metal complexes of κ superscript 3 cyclo tetrametaphosphate p subscript 4 o subscript 12 superscript 4 and cyclo trimetaphosphate p subscript 3 o subscript 9 superscript 3 |
| url | http://hdl.handle.net/1721.1/90949 https://orcid.org/0000-0003-2568-3269 |
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