{"title":"氟利昂溶液中六甲基磷三酰胺分子和离子氢键配合物的低温核磁共振结构","authors":"N.S. Golubev, S.F. Bureiko, G.S. Denisov","doi":"10.1016/0378-4487(82)80055-1","DOIUrl":null,"url":null,"abstract":"<div><p>The <sup>1</sup>H NMR spectra have been obtained for a number of H-bonded complexes formed by the interaction of OH-acids of increasing strength and [(CH<sub>3</sub>)<sub>2</sub>N]<sub>3</sub>PO (HMPT) in a freon mixture (CDF<sub>2</sub>Cl + CDFCl<sub>2</sub>) at 100 K.The signals of the complexes with moderately strong acids (pK<sub>a</sub>> −2) are singlets,which proves that they have a molecular structure,AH…B.With stronger acids,a doublet spin-spin coupling of the bridge proton with <sup>31</sup>P nucleus occurs (J<sub>PH</sub>=cca 20 Cps) indicating a complete proton transfer,A<sup>−</sup>…HB<sup>+</sup>.The conclusion has been drawn that a sharp change in structure is caused by gradual change in the interaction energy as measured by ΔpK<sub>a</sub>.The spectra of a number of conjugated complexes,[BHB]A<sup>−</sup>,have been taken.If B=B,the homoconjugated cation with a centrosymmetric H-bond is formed,followed by a strong decrease in J<sub>PH</sub>.</p></div>","PeriodicalId":100049,"journal":{"name":"Advances in Molecular Relaxation and Interaction Processes","volume":"24 4","pages":"Pages 225-231"},"PeriodicalIF":0.0000,"publicationDate":"1982-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0378-4487(82)80055-1","citationCount":"5","resultStr":"{\"title\":\"Structure of molecular and ionic H-bonded complexes of Hexamethylphosphortriamide by low temperature NMR in freon solution\",\"authors\":\"N.S. Golubev, S.F. Bureiko, G.S. Denisov\",\"doi\":\"10.1016/0378-4487(82)80055-1\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The <sup>1</sup>H NMR spectra have been obtained for a number of H-bonded complexes formed by the interaction of OH-acids of increasing strength and [(CH<sub>3</sub>)<sub>2</sub>N]<sub>3</sub>PO (HMPT) in a freon mixture (CDF<sub>2</sub>Cl + CDFCl<sub>2</sub>) at 100 K.The signals of the complexes with moderately strong acids (pK<sub>a</sub>> −2) are singlets,which proves that they have a molecular structure,AH…B.With stronger acids,a doublet spin-spin coupling of the bridge proton with <sup>31</sup>P nucleus occurs (J<sub>PH</sub>=cca 20 Cps) indicating a complete proton transfer,A<sup>−</sup>…HB<sup>+</sup>.The conclusion has been drawn that a sharp change in structure is caused by gradual change in the interaction energy as measured by ΔpK<sub>a</sub>.The spectra of a number of conjugated complexes,[BHB]A<sup>−</sup>,have been taken.If B=B,the homoconjugated cation with a centrosymmetric H-bond is formed,followed by a strong decrease in J<sub>PH</sub>.</p></div>\",\"PeriodicalId\":100049,\"journal\":{\"name\":\"Advances in Molecular Relaxation and Interaction Processes\",\"volume\":\"24 4\",\"pages\":\"Pages 225-231\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1982-12-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1016/0378-4487(82)80055-1\",\"citationCount\":\"5\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Advances in Molecular Relaxation and Interaction Processes\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/0378448782800551\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advances in Molecular Relaxation and Interaction Processes","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/0378448782800551","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Structure of molecular and ionic H-bonded complexes of Hexamethylphosphortriamide by low temperature NMR in freon solution
The 1H NMR spectra have been obtained for a number of H-bonded complexes formed by the interaction of OH-acids of increasing strength and [(CH3)2N]3PO (HMPT) in a freon mixture (CDF2Cl + CDFCl2) at 100 K.The signals of the complexes with moderately strong acids (pKa> −2) are singlets,which proves that they have a molecular structure,AH…B.With stronger acids,a doublet spin-spin coupling of the bridge proton with 31P nucleus occurs (JPH=cca 20 Cps) indicating a complete proton transfer,A−…HB+.The conclusion has been drawn that a sharp change in structure is caused by gradual change in the interaction energy as measured by ΔpKa.The spectra of a number of conjugated complexes,[BHB]A−,have been taken.If B=B,the homoconjugated cation with a centrosymmetric H-bond is formed,followed by a strong decrease in JPH.
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