1984
DOI: 10.1021/ja00326a044
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Proton-transfer kinetics in solids: tautomerism in free base porphines by nitrogen-15 CPMAS NMR

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Cited by 116 publications
(51 citation statements)
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“…Four distinct peaks were evident in the 15 N spectrum representing each of the four pyrrole nitrogens. That these peaks were below 180 ppm was consistent with all of these nitrogens being protonated at neutral pH (65,66). Interestingly, for Syn-Cph1(PAS-GAF-PHY) two of these peaks overlapped, indicative of similar chemical environments (32,33), whereas in SyB-Cph1(GAF) they were more uniformly resolved, indicative of more distinct chemical environments (Fig.…”
Section: Syn-cph1supporting
confidence: 52%
“…Four distinct peaks were evident in the 15 N spectrum representing each of the four pyrrole nitrogens. That these peaks were below 180 ppm was consistent with all of these nitrogens being protonated at neutral pH (65,66). Interestingly, for Syn-Cph1(PAS-GAF-PHY) two of these peaks overlapped, indicative of similar chemical environments (32,33), whereas in SyB-Cph1(GAF) they were more uniformly resolved, indicative of more distinct chemical environments (Fig.…”
Section: Syn-cph1supporting
confidence: 52%
“…In the future one might also use dipolar or quadrupolar interactions of protons or deuterons for the study of proton exchange reactions when anisotropic media such as liquid crystals are used as solvents. In addition to reactions in liquids, kinetic isotope effect studies of proton transfer processes in solids, for which some examples have already been given [35,43], might also be fruitful. The results presented in this study have shown that NMR studies of multiple kinetic isotope effects might be useful for the further development of the theory of kinetic isotope effects which has been initiated by Professor R. P. Bell and by Professor Ja cob Bigeleisen to whom this paper is dedicated at the occasion of his 70th birthday.…”
Section: Discussionmentioning
confidence: 99%
“…5 were analyzed using the ex change matrix of (35). Unfortunately, not all kinetic quantities t ahah^A HAD (D), r-1 L AHAD (D), and rADAD*(D) could be obtained for all values of D. This is obvious because AD does not contribute to the lineshape at D = 0.…”
Section: F Nmr Lineshape Analysis and Magnetization Transfer Of Dffmentioning
confidence: 99%
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“…[3j] These dramatic differences in the barrier (KSSE, kinetic solid-state effect) [24] are due to the structure of tropolone in the solid state, in which it forms two near planar dimers (12 2 , Figure 9 [25] The equilibrium between tropolone tautomers in the solid state involves not only a proton transfer (usually lower in the solid state due to tunneling effects) but a complete reorganisation of the molecule 12 2 in the crystal. Several authors have calculated the barrier for tropolone monomer 12, [3e,3g,3k] the most exhaustive work being that of Redington and Bock.…”
mentioning
confidence: 99%