Controlling the catalytic oligomerization of terminal alkynes promoted by organoactinides: A strategy to short oligomers

Ariel Haskel; Ji Quan Wang; Thomas Straub; Tal Gueta Neyroud; Moris S. Eisen

doi:10.1021/ja983640z

Controlling the catalytic oligomerization of terminal alkynes promoted by organoactinides: A strategy to short oligomers

Ariel Haskel, Ji Quan Wang, Thomas Straub, Tal Gueta Neyroud, Moris S. Eisen^*

^*Corresponding author for this work

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

80 Scopus citations

Abstract

A novel strategy has been developed for the catalytic synthesis of short oligomers, dimers and/or trimers, of terminal alkynes. The method allows control of the extent of and, in some cases, the regiospecificity in the catalyzed oligomerization of terminal alkynes promoted by bis(pentamethylcyclopentadienyl)actinide dimethyl complexes (Cp*₂AnMe₂; Cp* = C₅Me₅, An = Th, U). These metallocene precursors are known to promote the simultaneous production of a large number of differently sized oligomers in the presence of terminal alkynes. However, the addition of specific amines ensures the selective synthesis of short oligomers. Catalytic 'tailoring' to dimers or a mixture of dimers and trimers can be achieved by using nonbulky or bulky amines, respectively. The kinetics in the catalytic oligomerization of 1-hexyne, in the presence of i-BuNH₂, mediated by Cp*₂ThMe₂ are first order in [alkyne], first order in [Th], and inverse first order in [amine]. Kinetic, spectroscopic, and mechanistic data argue that the turnover-limiting step involves the formation of the mono(amido)thorium acetylide complex with rapid insertion of the alkyne and protonolysis by the amine.

Original language	English
Pages (from-to)	3025-3034
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	121
Issue number	13
DOIs	https://doi.org/10.1021/ja983640z
State	Published - 7 Apr 1999
Externally published	Yes

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title = "Controlling the catalytic oligomerization of terminal alkynes promoted by organoactinides: A strategy to short oligomers",

abstract = "A novel strategy has been developed for the catalytic synthesis of short oligomers, dimers and/or trimers, of terminal alkynes. The method allows control of the extent of and, in some cases, the regiospecificity in the catalyzed oligomerization of terminal alkynes promoted by bis(pentamethylcyclopentadienyl)actinide dimethyl complexes (Cp*2AnMe2; Cp* = C5Me5, An = Th, U). These metallocene precursors are known to promote the simultaneous production of a large number of differently sized oligomers in the presence of terminal alkynes. However, the addition of specific amines ensures the selective synthesis of short oligomers. Catalytic 'tailoring' to dimers or a mixture of dimers and trimers can be achieved by using nonbulky or bulky amines, respectively. The kinetics in the catalytic oligomerization of 1-hexyne, in the presence of i-BuNH2, mediated by Cp*2ThMe2 are first order in [alkyne], first order in [Th], and inverse first order in [amine]. Kinetic, spectroscopic, and mechanistic data argue that the turnover-limiting step involves the formation of the mono(amido)thorium acetylide complex with rapid insertion of the alkyne and protonolysis by the amine.",

author = "Ariel Haskel and Wang, {Ji Quan} and Thomas Straub and Neyroud, {Tal Gueta} and Eisen, {Moris S.}",

year = "1999",

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AU - Haskel, Ariel

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AU - Straub, Thomas

AU - Neyroud, Tal Gueta

AU - Eisen, Moris S.

PY - 1999/4/7

Y1 - 1999/4/7

N2 - A novel strategy has been developed for the catalytic synthesis of short oligomers, dimers and/or trimers, of terminal alkynes. The method allows control of the extent of and, in some cases, the regiospecificity in the catalyzed oligomerization of terminal alkynes promoted by bis(pentamethylcyclopentadienyl)actinide dimethyl complexes (Cp*2AnMe2; Cp* = C5Me5, An = Th, U). These metallocene precursors are known to promote the simultaneous production of a large number of differently sized oligomers in the presence of terminal alkynes. However, the addition of specific amines ensures the selective synthesis of short oligomers. Catalytic 'tailoring' to dimers or a mixture of dimers and trimers can be achieved by using nonbulky or bulky amines, respectively. The kinetics in the catalytic oligomerization of 1-hexyne, in the presence of i-BuNH2, mediated by Cp*2ThMe2 are first order in [alkyne], first order in [Th], and inverse first order in [amine]. Kinetic, spectroscopic, and mechanistic data argue that the turnover-limiting step involves the formation of the mono(amido)thorium acetylide complex with rapid insertion of the alkyne and protonolysis by the amine.

AB - A novel strategy has been developed for the catalytic synthesis of short oligomers, dimers and/or trimers, of terminal alkynes. The method allows control of the extent of and, in some cases, the regiospecificity in the catalyzed oligomerization of terminal alkynes promoted by bis(pentamethylcyclopentadienyl)actinide dimethyl complexes (Cp*2AnMe2; Cp* = C5Me5, An = Th, U). These metallocene precursors are known to promote the simultaneous production of a large number of differently sized oligomers in the presence of terminal alkynes. However, the addition of specific amines ensures the selective synthesis of short oligomers. Catalytic 'tailoring' to dimers or a mixture of dimers and trimers can be achieved by using nonbulky or bulky amines, respectively. The kinetics in the catalytic oligomerization of 1-hexyne, in the presence of i-BuNH2, mediated by Cp*2ThMe2 are first order in [alkyne], first order in [Th], and inverse first order in [amine]. Kinetic, spectroscopic, and mechanistic data argue that the turnover-limiting step involves the formation of the mono(amido)thorium acetylide complex with rapid insertion of the alkyne and protonolysis by the amine.

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Controlling the catalytic oligomerization of terminal alkynes promoted by organoactinides: A strategy to short oligomers

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