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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 language | English |
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Pages (from-to) | 14249-14256 |
Number of pages | 8 |
Journal | Dalton Transactions |
Volume | 43 |
Issue number | 38 |
Early online date | 9 Jan 2014 |
DOIs | |
Publication status | Published - 14 Oct 2014 |
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Dive into the research topics of 'Catalytic hydroacetylenation of carbodiimides with homoleptic alkaline earth hexamethyldisilazides'. Together they form a unique fingerprint.Projects
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Group 2: Elements of 21st Century Catalysis
Engineering and Physical Sciences Research Council
23/05/11 → 31/03/15
Project: Research council