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

13 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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Alkynes
Magnesium
magnesium
acetylene
calcium
trienes
Calcium
Dimerization
Deuterium
metathesis
alkynes
dimerization
methylene
Labeling
X ray diffraction analysis
Nuclear magnetic resonance spectroscopy
marking
Protons
deuterium
delivery

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Catalytic and stoichiometric cumulene formation within dimeric group 2 acetylides. / Arrowsmith, Merle; Crimmin, Mark R.; Hill, Michael S.; Lomas, Sarah L.; Macdougall, Dugald J.; Mahon, Mary F.

In: Organometallics, Vol. 32, No. 17, 09.09.2013, p. 4961-4972.

Research output: Contribution to journalArticle

Arrowsmith, Merle ; Crimmin, Mark R. ; Hill, Michael S. ; Lomas, Sarah L. ; Macdougall, Dugald J. ; Mahon, Mary F. / Catalytic and stoichiometric cumulene formation within dimeric group 2 acetylides. In: Organometallics. 2013 ; Vol. 32, No. 17. pp. 4961-4972.
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