Protio-2-propyl Dication (Propane Dication, C3H82+): Hydrogen/Deuterium Exchange and Theoretical Study. Differentiation of Reactive Gitonic (Proximal) from Stable Distonic (Distant) Dications and the Protosolvolytic Activation of Carbocations

George A. Olah; Nikolai Hartz; Golam Rasul; G. K. Surya Prakash; Maureen Burkhart; Koop Lammertsma

doi:10.1021/ja00087a003

Protio-2-propyl Dication (Propane Dication, C₃H₈²⁺): Hydrogen/Deuterium Exchange and Theoretical Study. Differentiation of Reactive Gitonic (Proximal) from Stable Distonic (Distant) Dications and the Protosolvolytic Activation of Carbocations

George A. Olah, Nikolai Hartz, Golam Rasul, G. K. Surya Prakash, Maureen Burkhart, Koop Lammertsma

Research output: Contribution to journal › Article › peer-review

33 Citations (Scopus)

Abstract

Hydrogen/deuterium exchange was observed by ²H-NMR spectroscopy for the long-lived 2-propyl cation when treated with DF in SbF₅/SO₂CIF at -78 °C. As under long-lived stable ion conditions at low temperatures no deprotonation equilibria exist for alkyl cations, protio (deuterio) solvation involving the intermediacy of the protio-(deuterio)-2-propyl dication is suggested to account for the exchange. Ab initio calculations at the MP4SDTQ/6-31G^**//MP2(FU)/6-31G^**level show the protio-2-propyl dication, a gitonic (proximal) dication (as contrasted with usual distonic (distant) dications), to be a remarkably stable minimum structure and support the suggested mechanism for the observed isotopic scrambling.

Original language	English
Pages (from-to)	3187-3191
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	116
Issue number	8
DOIs	https://doi.org/10.1021/ja00087a003
Publication status	Published - 1 Apr 1994
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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Olah, G. A., Hartz, N., Rasul, G., Surya Prakash, G. K., Burkhart, M., & Lammertsma, K. (1994). Protio-2-propyl Dication (Propane Dication, C₃H₈²⁺): Hydrogen/Deuterium Exchange and Theoretical Study. Differentiation of Reactive Gitonic (Proximal) from Stable Distonic (Distant) Dications and the Protosolvolytic Activation of Carbocations. Journal of the American Chemical Society, 116(8), 3187-3191. https://doi.org/10.1021/ja00087a003

Olah, George A. ; Hartz, Nikolai ; Rasul, Golam et al. / Protio-2-propyl Dication (Propane Dication, C₃H₈²⁺) : Hydrogen/Deuterium Exchange and Theoretical Study. Differentiation of Reactive Gitonic (Proximal) from Stable Distonic (Distant) Dications and the Protosolvolytic Activation of Carbocations. In: Journal of the American Chemical Society. 1994 ; Vol. 116, No. 8. pp. 3187-3191.

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title = "Protio-2-propyl Dication (Propane Dication, C3H82+): Hydrogen/Deuterium Exchange and Theoretical Study. Differentiation of Reactive Gitonic (Proximal) from Stable Distonic (Distant) Dications and the Protosolvolytic Activation of Carbocations",

abstract = "Hydrogen/deuterium exchange was observed by 2H-NMR spectroscopy for the long-lived 2-propyl cation when treated with DF in SbF5/SO2CIF at -78 °C. As under long-lived stable ion conditions at low temperatures no deprotonation equilibria exist for alkyl cations, protio (deuterio) solvation involving the intermediacy of the protio-(deuterio)-2-propyl dication is suggested to account for the exchange. Ab initio calculations at the MP4SDTQ/6-31G**//MP2(FU)/6-31G**level show the protio-2-propyl dication, a gitonic (proximal) dication (as contrasted with usual distonic (distant) dications), to be a remarkably stable minimum structure and support the suggested mechanism for the observed isotopic scrambling.",

author = "Olah, {George A.} and Nikolai Hartz and Golam Rasul and {Surya Prakash}, {G. K.} and Maureen Burkhart and Koop Lammertsma",

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Olah, GA, Hartz, N, Rasul, G, Surya Prakash, GK, Burkhart, M & Lammertsma, K 1994, 'Protio-2-propyl Dication (Propane Dication, C₃H₈²⁺): Hydrogen/Deuterium Exchange and Theoretical Study. Differentiation of Reactive Gitonic (Proximal) from Stable Distonic (Distant) Dications and the Protosolvolytic Activation of Carbocations', Journal of the American Chemical Society, vol. 116, no. 8, pp. 3187-3191. https://doi.org/10.1021/ja00087a003

Protio-2-propyl Dication (Propane Dication, C₃H₈²⁺): Hydrogen/Deuterium Exchange and Theoretical Study. Differentiation of Reactive Gitonic (Proximal) from Stable Distonic (Distant) Dications and the Protosolvolytic Activation of Carbocations. / Olah, George A.; Hartz, Nikolai; Rasul, Golam et al.
In: Journal of the American Chemical Society, Vol. 116, No. 8, 01.04.1994, p. 3187-3191.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Protio-2-propyl Dication (Propane Dication, C3H82+)

T2 - Hydrogen/Deuterium Exchange and Theoretical Study. Differentiation of Reactive Gitonic (Proximal) from Stable Distonic (Distant) Dications and the Protosolvolytic Activation of Carbocations

AU - Olah, George A.

AU - Hartz, Nikolai

AU - Rasul, Golam

AU - Surya Prakash, G. K.

AU - Burkhart, Maureen

AU - Lammertsma, Koop

PY - 1994/4/1

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N2 - Hydrogen/deuterium exchange was observed by 2H-NMR spectroscopy for the long-lived 2-propyl cation when treated with DF in SbF5/SO2CIF at -78 °C. As under long-lived stable ion conditions at low temperatures no deprotonation equilibria exist for alkyl cations, protio (deuterio) solvation involving the intermediacy of the protio-(deuterio)-2-propyl dication is suggested to account for the exchange. Ab initio calculations at the MP4SDTQ/6-31G**//MP2(FU)/6-31G**level show the protio-2-propyl dication, a gitonic (proximal) dication (as contrasted with usual distonic (distant) dications), to be a remarkably stable minimum structure and support the suggested mechanism for the observed isotopic scrambling.

AB - Hydrogen/deuterium exchange was observed by 2H-NMR spectroscopy for the long-lived 2-propyl cation when treated with DF in SbF5/SO2CIF at -78 °C. As under long-lived stable ion conditions at low temperatures no deprotonation equilibria exist for alkyl cations, protio (deuterio) solvation involving the intermediacy of the protio-(deuterio)-2-propyl dication is suggested to account for the exchange. Ab initio calculations at the MP4SDTQ/6-31G**//MP2(FU)/6-31G**level show the protio-2-propyl dication, a gitonic (proximal) dication (as contrasted with usual distonic (distant) dications), to be a remarkably stable minimum structure and support the suggested mechanism for the observed isotopic scrambling.

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Olah GA, Hartz N, Rasul G, Surya Prakash GK, Burkhart M, Lammertsma K. Protio-2-propyl Dication (Propane Dication, C₃H₈²⁺): Hydrogen/Deuterium Exchange and Theoretical Study. Differentiation of Reactive Gitonic (Proximal) from Stable Distonic (Distant) Dications and the Protosolvolytic Activation of Carbocations. Journal of the American Chemical Society. 1994 Apr 1;116(8):3187-3191. doi: 10.1021/ja00087a003