Catalytic and stoichiometric cumulene formation within dimeric group 2 acetylides

Merle Arrowsmith, Mark R. Crimmin, Michael S. Hill, Sarah L. Lomas, Dugald J. Macdougall, Mary F. Mahon

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

A series of β-diketiminate-supported magnesium and calcium acetylide complexes have been synthesized by σ-bond metathesis of magnesium n-butyl or magnesium and calcium amido precursors and a range of terminal acetylenes. The dimeric complexes have been characterized by NMR spectroscopy and X-ray diffraction analysis. The homoleptic bis(amido) and dialkyl complexes [M{X(SiMe3)2}2(THF)2] (M = Ca, Sr; X = N, CH) have been assessed for the atom-efficient, catalytic head-to-head dimerization of donor-functionalized terminal alkynes into butatrienes and aryl-/silyl-substituted terminal acetylenes into 1,3-enynes. Deuterium labeling studies of the catalytic reactions are suggested to imply that triene formation requires concerted proton delivery and rearrangement via an adjacent methylene group at a bimetallic alkaline-earth species.
Original languageEnglish
Pages (from-to)4961-4972
Number of pages12
JournalOrganometallics
Volume32
Issue number17
Early online date22 Aug 2013
DOIs
Publication statusPublished - 9 Sep 2013

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