Structural and metal–halogen exchange reactivity studies of sodium magnesiate biphenolate complexes
| Autor: | Ross McLellan, Alan R. Kennedy, Michael Fairley, Sabrina Touchet, Antonio J. Martínez-Martínez, Philippe C. Gros, Callum Yeardley, Charles T. O'Hara |
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| Přispěvatelé: | WestCHEM, University of Glasgow, Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Laboratorio de Catalisis Homogenea, Unidad Asociada al CSIC CIQSO-Centro de Investigacion en Quimica Sostenible and Departamento de Quimica, Universidad de Huelva, Universidad de Huelva |
| Rok vydání: | 2020 |
| Předmět: |
010405 organic chemistry
Ligand Magnesium Aryl Sodium chemistry.chemical_element 010402 general chemistry 01 natural sciences Medicinal chemistry Toluene 0104 chemical sciences Inorganic Chemistry Solvent chemistry.chemical_compound chemistry Halogen [CHIM.CRIS]Chemical Sciences/Cristallography [CHIM]Chemical Sciences QD [CHIM.COOR]Chemical Sciences/Coordination chemistry Reactivity (chemistry) |
| Zdroj: | Dalton Transactions Dalton Transactions, Royal Society of Chemistry, 2020, pp.5257-5263. ⟨10.1039/d0dt00904k⟩ |
| ISSN: | 1477-9234 1477-9226 |
| DOI: | 10.1039/d0dt00904k |
| Popis: | International audience; Bimetallic sodium magnesiates have been employed in metal-halogen exchange for the first time. Utilising the racemic phenoxide ligand 5,5´,6,6´-tetramethyl-3,3´-di-tert-butyl-1,1´-biphenyl-2,2´-diol [(rac)-BIPHEN-H 2 ], the dialkyl sodium magnesiates [(rac)-BIPHEN]Na 2 MgBu 2 (TMEDA) 2 3 and [(rac)-BIPHEN]Na 2 MgBu 2 (PMDETA) 2 4 have been synthesised. Both 3 and 4 can be easily prepared through co-complexation of din -butylmagnesium with the sodiated (rac)-BIPHEN precursor which can be prepared in situ in hydrocarbon solvent. Prior to the main investigation, synthesis of the sodiated precursor [BIPHEN] 2 Na 4 (THF) 4 1 was explored in order to better understand the formation of sodium magnesiates utilising the dianionic (rac)-BIPHEN ligand as the parent ligand. In addition, a BIPHEN-rich sodium magnesiate [BIPHEN] 2 Na 2 Mg(THF) 4 2 was prepared and characterised, and its formation was rationalised. Complex 1 and 4 have also been fully characterised in both solid and solution state. In terms of onward reactivity, 3 and 4 have been tested as potential exchange reagents with aryl and heteroaryl iodides to produce aryl and heteroaryl magnesium phenoxides utilising toluene as a non-polar hydrocarbon solvent. Complex 3 reacted smoothly to give a range of aryl and heteroaryl magnesium phenoxides, whilst 4's reactivity is more sluggish. |
| Databáze: | OpenAIRE |
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