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Issue 38, 2014
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Catalytic hydroacetylenation of carbodiimides with homoleptic alkaline earth hexamethyldisilazides

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Abstract

The homoleptic alkaline earth hexamethyldisilazides, [M{N(SiMe3)2}2(THF)2] (M = Mg 1a; Ca 1b; Sr 1c), have been shown to act as efficient precatalysts for the hydroacetylenation of organic carbodiimides with alkyl- and arylacetylenes. Catalytic activity was observed to increase with the size of the group 2 metal centre employed and to be strongly influenced by the steric properties of the carbodiimide substrate. The intermediate dimeric calcium and strontium bis(amidinate) complexes, [{PhC[triple bond, length as m-dash]CC(NiPr)2}2M]2 (M = Ca 2b, Sr 2c), have been isolated and crystallographically characterised. Kinetic studies using the strontium precursor, 1c, provided a reaction rate law independent of [acetylene] but proportional to [carbodiimide]2 and inversely proportional to the concentration of the amidine product in solution.

Graphical abstract: Catalytic hydroacetylenation of carbodiimides with homoleptic alkaline earth hexamethyldisilazides

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Publication details

The article was received on 17 Dec 2013, accepted on 08 Jan 2014 and first published on 09 Jan 2014


Article type: Paper
DOI: 10.1039/C3DT53542H
Citation: Dalton Trans., 2014,43, 14249-14256
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    Catalytic hydroacetylenation of carbodiimides with homoleptic alkaline earth hexamethyldisilazides

    M. Arrowsmith, M. R. Crimmin, M. S. Hill, S. L. Lomas, M. S. Heng, P. B. Hitchcock and G. Kociok-Köhn, Dalton Trans., 2014, 43, 14249
    DOI: 10.1039/C3DT53542H

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