Oligomerization of alkynes by the RhCl3-aliquat 336 catalyst system. Part 1. Formation of benzene derivatives

Ibrahim Amer; Tamar Bernstein; Moris Eisen; Jochanan Blum; K. Peter C. Vollhardt

doi:10.1016/0304-5102(90)85254-F

Oligomerization of alkynes by the RhCl₃-aliquat 336 catalyst system. Part 1. Formation of benzene derivatives

Ibrahim Amer^*, Tamar Bernstein, Moris Eisen, Jochanan Blum, K. Peter C. Vollhardt

^*Corresponding author for this work

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

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Abstract

The cyclo-oligomerization of several terminal and internal alkynes under phase transfer conditions by the RhCl₃-Aliquat® 336 catalyst is described. The kinetics of 1-heptyne cyclotrimerization at 90 °C in 1,1,2,2-tetrachloroethane/water were found to follow the second-order rate law d[arene]/dt = -k[alkyne][RhCl₃] when the molar ratio of substrate:rhodium chloride:quat was approximately 25:1:1. The activation energy of E_a = 12.5 kcal mol^-1 suggests that the catalysis is both chemically and diffusion controlled. Product analysis is compatible with a mechanism that involves rhodacyclopentadiene rather than metal cyclobutadiene intermediates.

Original language	English
Pages (from-to)	313-321
Number of pages	9
Journal	Journal of Molecular Catalysis
Volume	60
Issue number	3
DOIs	https://doi.org/10.1016/0304-5102(90)85254-F
State	Published - 1 Jul 1990
Externally published	Yes

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title = "Oligomerization of alkynes by the RhCl3-aliquat 336 catalyst system. Part 1. Formation of benzene derivatives",

abstract = "The cyclo-oligomerization of several terminal and internal alkynes under phase transfer conditions by the RhCl3-Aliquat{\textregistered} 336 catalyst is described. The kinetics of 1-heptyne cyclotrimerization at 90 °C in 1,1,2,2-tetrachloroethane/water were found to follow the second-order rate law d[arene]/dt = -k[alkyne][RhCl3] when the molar ratio of substrate:rhodium chloride:quat was approximately 25:1:1. The activation energy of Ea = 12.5 kcal mol-1 suggests that the catalysis is both chemically and diffusion controlled. Product analysis is compatible with a mechanism that involves rhodacyclopentadiene rather than metal cyclobutadiene intermediates.",

author = "Ibrahim Amer and Tamar Bernstein and Moris Eisen and Jochanan Blum and Vollhardt, {K. Peter C.}",

note = "Funding Information: This research was supported by grant No. 86-00013/l from the U.S.-Israel Binational Science Foundation (BSF), Jerusalem, Israel, and by the Director, Office of Energy Research, Office of Basic Energy Sciences, Materials Science Division of the U.S.D.E. under contract DE-AC-OS-76SF00098.",

year = "1990",

month = jul,

day = "1",

doi = "10.1016/0304-5102(90)85254-F",

language = "英语",

volume = "60",

pages = "313--321",

journal = "Journal of Molecular Catalysis",

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number = "3",

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T1 - Oligomerization of alkynes by the RhCl3-aliquat 336 catalyst system. Part 1. Formation of benzene derivatives

AU - Amer, Ibrahim

AU - Bernstein, Tamar

AU - Eisen, Moris

AU - Blum, Jochanan

AU - Vollhardt, K. Peter C.

N1 - Funding Information: This research was supported by grant No. 86-00013/l from the U.S.-Israel Binational Science Foundation (BSF), Jerusalem, Israel, and by the Director, Office of Energy Research, Office of Basic Energy Sciences, Materials Science Division of the U.S.D.E. under contract DE-AC-OS-76SF00098.

PY - 1990/7/1

Y1 - 1990/7/1

N2 - The cyclo-oligomerization of several terminal and internal alkynes under phase transfer conditions by the RhCl3-Aliquat® 336 catalyst is described. The kinetics of 1-heptyne cyclotrimerization at 90 °C in 1,1,2,2-tetrachloroethane/water were found to follow the second-order rate law d[arene]/dt = -k[alkyne][RhCl3] when the molar ratio of substrate:rhodium chloride:quat was approximately 25:1:1. The activation energy of Ea = 12.5 kcal mol-1 suggests that the catalysis is both chemically and diffusion controlled. Product analysis is compatible with a mechanism that involves rhodacyclopentadiene rather than metal cyclobutadiene intermediates.

AB - The cyclo-oligomerization of several terminal and internal alkynes under phase transfer conditions by the RhCl3-Aliquat® 336 catalyst is described. The kinetics of 1-heptyne cyclotrimerization at 90 °C in 1,1,2,2-tetrachloroethane/water were found to follow the second-order rate law d[arene]/dt = -k[alkyne][RhCl3] when the molar ratio of substrate:rhodium chloride:quat was approximately 25:1:1. The activation energy of Ea = 12.5 kcal mol-1 suggests that the catalysis is both chemically and diffusion controlled. Product analysis is compatible with a mechanism that involves rhodacyclopentadiene rather than metal cyclobutadiene intermediates.

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DO - 10.1016/0304-5102(90)85254-F

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SN - 0304-5102

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JO - Journal of Molecular Catalysis

JF - Journal of Molecular Catalysis

IS - 3

ER -

Oligomerization of alkynes by the RhCl₃-aliquat 336 catalyst system. Part 1. Formation of benzene derivatives

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