Catalytic hydroacetylenation of carbodiimides with homoleptic alkaline earth hexamethyldisilazides

Autor:	Myra Sae Heng, Peter B. Hitchcock, Gabriele Kociok-Köhn, Merle Arrowsmith, Mark R. Crimmin, Sarah L. Lomas, Michael S. Hill
Rok vydání:	2014
Předmět:	chemistry.chemical_classification Alkaline earth metal Strontium Chemistry Inorganic chemistry chemistry.chemical_element Medicinal chemistry Catalysis Inorganic Chemistry Amidine chemistry.chemical_compound Acetylene Homoleptic Alkyl Carbodiimide
Zdroj:	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, vol. 43, no. 38, pp. 14249-14256 . https://doi.org/10.1039/c3dt53542h
ISSN:	1477-9234 1477-9226
DOI:	10.1039/c3dt53542h
Popis:	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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::5947250038b1a2653289e2209574e1fa https://doi.org/10.1039/c3dt53542h Zobrazit plný text záznamu