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, G. Kociok-Köhn

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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, [{PhCCC(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.

Original languageEnglish
Pages (from-to)14249-14256
Number of pages8
JournalDalton Transactions
Volume43
Issue number38
Early online date9 Jan 2014
DOIs
Publication statusPublished - 14 Oct 2014

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Carbodiimides
Strontium
Earth (planet)
Amidines
Acetylene
Reaction rates
Catalyst activity
Metals
Calcium
Kinetics
Substrates

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Arrowsmith, M., Crimmin, M. R., Hill, M. S., Lomas, S. L., Heng, M. S., Hitchcock, P. B., & Kociok-Köhn, G. (2014). Catalytic hydroacetylenation of carbodiimides with homoleptic alkaline earth hexamethyldisilazides. Dalton Transactions, 43(38), 14249-14256. https://doi.org/10.1039/c3dt53542h

Catalytic hydroacetylenation of carbodiimides with homoleptic alkaline earth hexamethyldisilazides. / Arrowsmith, M.; Crimmin, M.R.; Hill, M.S.; Lomas, S.L.; Heng, M.S.; Hitchcock, P.B.; Kociok-Köhn, G.

In: Dalton Transactions, Vol. 43, No. 38, 14.10.2014, p. 14249-14256.

Research output: Contribution to journalArticle

Arrowsmith, M, Crimmin, MR, Hill, MS, Lomas, SL, Heng, MS, Hitchcock, PB & Kociok-Köhn, G 2014, 'Catalytic hydroacetylenation of carbodiimides with homoleptic alkaline earth hexamethyldisilazides', Dalton Transactions, vol. 43, no. 38, pp. 14249-14256. https://doi.org/10.1039/c3dt53542h
Arrowsmith, M. ; Crimmin, M.R. ; Hill, M.S. ; Lomas, S.L. ; Heng, M.S. ; Hitchcock, P.B. ; Kociok-Köhn, G. / Catalytic hydroacetylenation of carbodiimides with homoleptic alkaline earth hexamethyldisilazides. In: Dalton Transactions. 2014 ; Vol. 43, No. 38. pp. 14249-14256.
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