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Structural and metal-halogen exchange reactivity studies of sodium magnesiate biphenolate complexes
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-H2], the dialkyl sodium magnesiates [(rac)-BIPHEN]Na2MgBu2(TMEDA)23 and [(rac)-BIPHEN]Na2MgBu2(PMDETA)24 have been synthesised. Both 3 and 4 can be easily prepared through co-complexation of di-n-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]2Na4(THF)41 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]2Na2Mg(THF)42 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.
Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. Product Details of 3030-47-5, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 3030-47-5, in my other articles.
Reference：
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI