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 journalArticlepeer-review

76 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 languageEnglish
Pages (from-to)3025-3034
Number of pages10
JournalJournal of the American Chemical Society
Volume121
Issue number13
DOIs
StatePublished - 7 Apr 1999
Externally publishedYes

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