Dihydrogen Tetrametaphosphate, [P[subscript 4]O][subscript 12]H[subscript 2]][superscript 2] –: Synthesis, Solubilization in Organic Media, Preparation of its Anhydride [P[subscript 4]O[subscript 11]][superscript 2] – and Acidic Methyl Ester, and Conversion to Tetrametaphosphate Metal Complexes via Protonolysis
Dihydrogen tetrametaphosphate [P[subscript 4]O[subscript 12]H[subscript 2]] [superscript 2]- (1) can now be synthesized and isolated as its PPN salt ([PPN] + = [N(PPh[subscript 3])[subscript 2]][superscript +]) via treatment of [PPN][subscript 4 ][P[subscript 4]O[subscript 12]] with trifluoroacetic...
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American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/113228 https://orcid.org/0000-0003-3497-181X https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 |
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| author | Marino, Nadia Jiang, Yanfeng Chakarawet, Khetpakorn Kohout, Andrea Laura Nava, Matthew Jordan Cummins, Christopher C |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Marino, Nadia Jiang, Yanfeng Chakarawet, Khetpakorn Kohout, Andrea Laura Nava, Matthew Jordan Cummins, Christopher C |
| author_sort | Marino, Nadia |
| collection | MIT |
| description | Dihydrogen tetrametaphosphate [P[subscript 4]O[subscript 12]H[subscript 2]] [superscript 2]- (1) can now be synthesized and isolated as its PPN salt ([PPN] + = [N(PPh[subscript 3])[subscript 2]][superscript +]) via treatment of [PPN][subscript 4 ][P[subscript 4]O[subscript 12]] with trifluoroacetic anhydride in wet acetone; this simple procedure affords the oxoacid salt in 94% yield. A pK a of 15.83 ± 0.11 in acetonitrile was determined. [P[subscript 4]O[subscript 12]H[subscript 2]][subscript 2-] reacts with the dehydrating agent N,N′-dicyclohexylcarbodiimide to afford tetrametaphosphate anhydride [P[subscript 4]O[subscript 11]][subscript 2-] (2) in 82% yield, also as the PPN salt. From 2 a monohydrogen tetrametaphosphate ester [P[subscript 4]O[subscript 10] (OH)(OMe)][superscript 2-] (3, 96%) was derived by addition of methanol, illustrating that 2 can function as a reagent for chemical phosphorylation. Addition of water to 2 regenerates 1 quantitatively. Deprotonation of 1 by metal amides in the +2 oxidation state led to the unconventional monomeric tin(II) κ[superscript 4] tetrametaphosphate [Sn(P [subscript 4]O[subscript 12])] [superscript 2-] (4, 78%, a molecular analog of SnO) and binary dimeric chromium(II) bis(μ[subscript 2] ,κ[superscript 2], κ[superscript 2]) derivative [Cr[subscript 2](P[subscript 4]O[subscript 12])[subscript 2]][superscript 4-] (5, 82%). Structural data stemming from single-crystal X-ray diffraction studies for the PPN salts of anions 1-5 are also reported. |
| first_indexed | 2024-09-23T15:43:45Z |
| format | Article |
| id | mit-1721.1/113228 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T15:43:45Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1132282022-10-02T03:41:17Z Dihydrogen Tetrametaphosphate, [P[subscript 4]O][subscript 12]H[subscript 2]][superscript 2] –: Synthesis, Solubilization in Organic Media, Preparation of its Anhydride [P[subscript 4]O[subscript 11]][superscript 2] – and Acidic Methyl Ester, and Conversion to Tetrametaphosphate Metal Complexes via Protonolysis Marino, Nadia Jiang, Yanfeng Chakarawet, Khetpakorn Kohout, Andrea Laura Nava, Matthew Jordan Cummins, Christopher C Massachusetts Institute of Technology. Department of Chemistry Jiang, Yanfeng Chakarawet, Khetpakorn Kohout, Andrea Laura Nava, Matthew Jordan Cummins, Christopher C Dihydrogen tetrametaphosphate [P[subscript 4]O[subscript 12]H[subscript 2]] [superscript 2]- (1) can now be synthesized and isolated as its PPN salt ([PPN] + = [N(PPh[subscript 3])[subscript 2]][superscript +]) via treatment of [PPN][subscript 4 ][P[subscript 4]O[subscript 12]] with trifluoroacetic anhydride in wet acetone; this simple procedure affords the oxoacid salt in 94% yield. A pK a of 15.83 ± 0.11 in acetonitrile was determined. [P[subscript 4]O[subscript 12]H[subscript 2]][subscript 2-] reacts with the dehydrating agent N,N′-dicyclohexylcarbodiimide to afford tetrametaphosphate anhydride [P[subscript 4]O[subscript 11]][subscript 2-] (2) in 82% yield, also as the PPN salt. From 2 a monohydrogen tetrametaphosphate ester [P[subscript 4]O[subscript 10] (OH)(OMe)][superscript 2-] (3, 96%) was derived by addition of methanol, illustrating that 2 can function as a reagent for chemical phosphorylation. Addition of water to 2 regenerates 1 quantitatively. Deprotonation of 1 by metal amides in the +2 oxidation state led to the unconventional monomeric tin(II) κ[superscript 4] tetrametaphosphate [Sn(P [subscript 4]O[subscript 12])] [superscript 2-] (4, 78%, a molecular analog of SnO) and binary dimeric chromium(II) bis(μ[subscript 2] ,κ[superscript 2], κ[superscript 2]) derivative [Cr[subscript 2](P[subscript 4]O[subscript 12])[subscript 2]][superscript 4-] (5, 82%). Structural data stemming from single-crystal X-ray diffraction studies for the PPN salts of anions 1-5 are also reported. Swiss National Science Foundation 2018-01-19T14:44:46Z 2018-01-19T14:44:46Z 2014-08 2014-06 2018-01-18T19:25:29Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/113228 Jiang, Yanfeng, et al. “Dihydrogen Tetrametaphosphate, [P[subscript 4]O[subscript 12]H[subscript 2]][superscript 2]– : Synthesis, Solubilization in Organic Media, Preparation of Its Anhydride [P[subscript 4]O[subscript 11]] [superscript 2-] and Acidic Methyl Ester, and Conversion to Tetrametaphosphate Metal Complexes via Protonolysis.” Journal of the American Chemical Society, vol. 136, no. 34, Aug. 2014, pp. 11894–97. © 2014 American Chemical Society https://orcid.org/0000-0003-3497-181X https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 http://dx.doi.org/10.1021/JA5058339 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Marino, Nadia Jiang, Yanfeng Chakarawet, Khetpakorn Kohout, Andrea Laura Nava, Matthew Jordan Cummins, Christopher C Dihydrogen Tetrametaphosphate, [P[subscript 4]O][subscript 12]H[subscript 2]][superscript 2] –: Synthesis, Solubilization in Organic Media, Preparation of its Anhydride [P[subscript 4]O[subscript 11]][superscript 2] – and Acidic Methyl Ester, and Conversion to Tetrametaphosphate Metal Complexes via Protonolysis |
| title | Dihydrogen Tetrametaphosphate, [P[subscript 4]O][subscript 12]H[subscript 2]][superscript 2] –: Synthesis, Solubilization in Organic Media, Preparation of its Anhydride [P[subscript 4]O[subscript 11]][superscript 2] – and Acidic Methyl Ester, and Conversion to Tetrametaphosphate Metal Complexes via Protonolysis |
| title_full | Dihydrogen Tetrametaphosphate, [P[subscript 4]O][subscript 12]H[subscript 2]][superscript 2] –: Synthesis, Solubilization in Organic Media, Preparation of its Anhydride [P[subscript 4]O[subscript 11]][superscript 2] – and Acidic Methyl Ester, and Conversion to Tetrametaphosphate Metal Complexes via Protonolysis |
| title_fullStr | Dihydrogen Tetrametaphosphate, [P[subscript 4]O][subscript 12]H[subscript 2]][superscript 2] –: Synthesis, Solubilization in Organic Media, Preparation of its Anhydride [P[subscript 4]O[subscript 11]][superscript 2] – and Acidic Methyl Ester, and Conversion to Tetrametaphosphate Metal Complexes via Protonolysis |
| title_full_unstemmed | Dihydrogen Tetrametaphosphate, [P[subscript 4]O][subscript 12]H[subscript 2]][superscript 2] –: Synthesis, Solubilization in Organic Media, Preparation of its Anhydride [P[subscript 4]O[subscript 11]][superscript 2] – and Acidic Methyl Ester, and Conversion to Tetrametaphosphate Metal Complexes via Protonolysis |
| title_short | Dihydrogen Tetrametaphosphate, [P[subscript 4]O][subscript 12]H[subscript 2]][superscript 2] –: Synthesis, Solubilization in Organic Media, Preparation of its Anhydride [P[subscript 4]O[subscript 11]][superscript 2] – and Acidic Methyl Ester, and Conversion to Tetrametaphosphate Metal Complexes via Protonolysis |
| title_sort | dihydrogen tetrametaphosphate p subscript 4 o subscript 12 h subscript 2 superscript 2 synthesis solubilization in organic media preparation of its anhydride p subscript 4 o subscript 11 superscript 2 and acidic methyl ester and conversion to tetrametaphosphate metal complexes via protonolysis |
| url | http://hdl.handle.net/1721.1/113228 https://orcid.org/0000-0003-3497-181X https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 |
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