The 2-vinylphosphirane-3-phospholene rearrangement: Biradicaloid and concerted features

Maurice J. Van Eis; Tom Nijbacker; Franciscus J.J. De Kanter; Willem H. De Wolf; Koop Lammertsma; Friedrich Bickelhaupt

doi:10.1021/ja993829q

The 2-vinylphosphirane-3-phospholene rearrangement: Biradicaloid and concerted features

Maurice J. Van Eis, Tom Nijbacker, Franciscus J.J. De Kanter, Willem H. De Wolf, Koop Lammertsma, Friedrich Bickelhaupt

Vrije Universiteit Amsterdam

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

24 Citations (Scopus)

Abstract

Activation parameters have been determined for the 2-vinylphosphirane-3- phospholene rearrangement in the cycloheptane annellated series 7 → 8. For the thermal reaction, the mean activation parameters (ΔH(+) = 125 ± 5 kJ mol^-1 and ΔS(+) = -1 ± 14 J K^-1 mol^-1) are as expected for a biradicaloid character of the transition structure. In the presence of Cu(I) as a catalyst, the activation parameters for this conversion (ΔH(+) = 80.2 ± 3 kJ mol^-1 and ΔS(+) = -100 ± 7 J K^-1 mol^-1) are strikingly different and more in line with a concerted pathway.

Original language	English
Pages (from-to)	3033-3036
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	122
Issue number	13
DOIs	https://doi.org/10.1021/ja993829q
Publication status	Published - 5 Apr 2000
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "The 2-vinylphosphirane-3-phospholene rearrangement: Biradicaloid and concerted features",

abstract = "Activation parameters have been determined for the 2-vinylphosphirane-3- phospholene rearrangement in the cycloheptane annellated series 7 → 8. For the thermal reaction, the mean activation parameters (ΔH(+) = 125 ± 5 kJ mol-1 and ΔS(+) = -1 ± 14 J K-1 mol-1) are as expected for a biradicaloid character of the transition structure. In the presence of Cu(I) as a catalyst, the activation parameters for this conversion (ΔH(+) = 80.2 ± 3 kJ mol-1 and ΔS(+) = -100 ± 7 J K-1 mol-1) are strikingly different and more in line with a concerted pathway.",

author = "{Van Eis}, {Maurice J.} and Tom Nijbacker and {De Kanter}, {Franciscus J.J.} and {De Wolf}, {Willem H.} and Koop Lammertsma and Friedrich Bickelhaupt",

year = "2000",

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doi = "10.1021/ja993829q",

language = "English",

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TY - JOUR

T1 - The 2-vinylphosphirane-3-phospholene rearrangement

T2 - Biradicaloid and concerted features

AU - Van Eis, Maurice J.

AU - Nijbacker, Tom

AU - De Kanter, Franciscus J.J.

AU - De Wolf, Willem H.

AU - Lammertsma, Koop

AU - Bickelhaupt, Friedrich

PY - 2000/4/5

Y1 - 2000/4/5

N2 - Activation parameters have been determined for the 2-vinylphosphirane-3- phospholene rearrangement in the cycloheptane annellated series 7 → 8. For the thermal reaction, the mean activation parameters (ΔH(+) = 125 ± 5 kJ mol-1 and ΔS(+) = -1 ± 14 J K-1 mol-1) are as expected for a biradicaloid character of the transition structure. In the presence of Cu(I) as a catalyst, the activation parameters for this conversion (ΔH(+) = 80.2 ± 3 kJ mol-1 and ΔS(+) = -100 ± 7 J K-1 mol-1) are strikingly different and more in line with a concerted pathway.

AB - Activation parameters have been determined for the 2-vinylphosphirane-3- phospholene rearrangement in the cycloheptane annellated series 7 → 8. For the thermal reaction, the mean activation parameters (ΔH(+) = 125 ± 5 kJ mol-1 and ΔS(+) = -1 ± 14 J K-1 mol-1) are as expected for a biradicaloid character of the transition structure. In the presence of Cu(I) as a catalyst, the activation parameters for this conversion (ΔH(+) = 80.2 ± 3 kJ mol-1 and ΔS(+) = -100 ± 7 J K-1 mol-1) are strikingly different and more in line with a concerted pathway.

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U2 - 10.1021/ja993829q

DO - 10.1021/ja993829q

M3 - Article

AN - SCOPUS:0034607377

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JF - Journal of the American Chemical Society

IS - 13

ER -

The 2-vinylphosphirane-3-phospholene rearrangement: Biradicaloid and concerted features

Abstract

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